TW201222146A - Lithography copolymer and method of manufacturing the same, resist composition, patterned substrate manufacturing method, copolymer evaluation method, and copolymer composition analyzing method - Google Patents

Lithography copolymer and method of manufacturing the same, resist composition, patterned substrate manufacturing method, copolymer evaluation method, and copolymer composition analyzing method Download PDF

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TW201222146A
TW201222146A TW100137365A TW100137365A TW201222146A TW 201222146 A TW201222146 A TW 201222146A TW 100137365 A TW100137365 A TW 100137365A TW 100137365 A TW100137365 A TW 100137365A TW 201222146 A TW201222146 A TW 201222146A
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monomer
composition
copolymer
unit
ratio
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TW100137365A
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TWI540383B (en
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Atsushi Yasuda
Tomoya Oshikiri
Hikaru Momose
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Mitsubishi Rayon Co
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    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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Abstract

A target variate analysis unit (11) obtains a target variate by calculating a triad fraction of monomeric unit in the composition of a known copolymer sample on the basis of a copolymerization reaction ratio of the monomeric unit. A waveform processing unit (12) performs NMR measurement and processes a signal or the like. An explanatory variate analysis unit (13) obtains an explanatory variate of the known sample. A model creation unit (14) obtains a regression model of the target variate and the explanatory variate. A sample analysis unit (15) calculates a triad fraction of an unknown sample using the regression model on the basis of the unknown copolymer sample. Accordingly, it is possible to manufacture a resist composition with excellent solubility and sensitivity by using a lithography copolymer which has a total of triad fractions obtained in the above-described way equal to or less than 20 mol% in copolymer.

Description

201222146 ^t^AOOpif 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種微影製程用共聚合物及其製造方 法、抗餘劑組成物、形成有圖案的基板的製造方法、共聚 合物的評價方法、以及共聚合物組成分析方法。 本案是基於2010年10月18日於日本申請的日本專利 特願2010_233754號以及日本專利特願2〇1〇_233884號並201222146 ^t^AOOpif VI. [Technical Field] The present invention relates to a lithographic process copolymer, a method for producing the same, a composition for resisting residues, a method for producing a substrate on which a pattern is formed, A method for evaluating a copolymer and a method for analyzing a composition of a copolymer. This case is based on the Japanese Patent Application No. 2010_233754 filed on October 18, 2010 in Japan and the Japanese Patent Special Purpose No. 2〇1〇_233884.

主張優先權’且將其内容引用於本案中。 【先前技術】 通常，為了於聚合反應器系統中在線測定聚合物 (polymer) ’特別是共聚合物的性質，並控制聚合反應， 必需對該些聚合物的經測定的性質進行分析。 例如，可考慮作為共聚合物的一種的抗蝕劑（抗蝕劑 用、、且成物）的特性評價等，該抗㈣彳是半導體元件的製造 過程中所使用的微影製程用的組成物。 於半導體元件、液晶元件等的製造步驟中，近年來， =微影製，_形成的微細化迅速發展。作為該微細 E方法’ *_形成時對抗侧所照射的照射光的短 微旦枯Ϊ在研究導人ΚΓΡ準分子雷射（波長：248 nm) ArF準分子卜’正在研究謀求進-步的短波長化的 分子f射彳波長：2 : W η")微影製程技術及EUV準 这n 13·5ηηι)微影製程技術。 作為可較佳地對應於照射光的短波長化及 5 201222146 圖案的微細化的抗蝕劑組成物，提出有含有酸脫離性美藉 由酸的作用脫離而成為鹼可溶性的聚合物、及光酸產 的m胃的化學增幅型抗_組成物’且正進行該組成物的 開發及改良。 二作為ArF準分子雷射微影製程中所使用的化學増幅型 抗钱劑用聚合物，對於波長193 nm的光為透明的^稀酸 系聚合物受到矚目。 該丙烯酸系聚合物使用（A)酯鍵結有具有内酯環的 脂環式烴基的（曱基）丙烯酸酯、（B)酯鍵結有可藉由酸的 作用而脫離的基的（曱基）丙烯酸酯、以及（c)酯鍵結有具 有極性的取代基的烴基或含氧原子的雜環基的（甲基丙^ 酸酯作為單體而成的抗蝕劑用的共聚合物已有記載（例 如，參照專利文獻1 )。 然而，（曱基）丙烯酸酯的聚合物通常藉由自由基聚人 法來進行聚合。 土 Λ 〇 通常，於有2種以上的單體的多元系聚合物中，各單 體間的共聚合反應性比不同，因此在聚合初期與聚合後期 所生成的聚合物的共聚合組成比不同，所獲得的聚合物變 得具有組成分布。 若共聚合物中的單體單元的組成比存在偏差，則對於 溶劑的溶解性容易變低，當製備抗蝕劑組成物時，使其溶 解於溶劑中需要長時間、或者產生不溶物，因此存在^造 步驟數增加等對抗蝕劑組成物的製備帶來障礙的情況。= 外，所獲得的抗蝕劑組成物的感光度容易變得不充分。 201222146f 另外，通常於多元系聚合物中，鏈的規則性對應於各 單體間的共聚合反應性比而不同。具有許多各單體單元連 續，排列而成的_共聚合物容易使抗侧性能下降，因 此尋求-種減少了單體單元連續地排列而成的鏈的共聚合 物。 口 針對該些問題，例如記載有為了獲得具有高解析度的 抗蝕劑，使聚合速度相對較快的單體與相對較慢的單體的 籲躲神於前步驟與後步财變化，崎得共聚合組成分 布狹小的共聚合物的方法（例如，參照專利文獻2及 文獻3)。 藉由專利文獻2及專利文獻3的方法所製造的抗蝕劑 用共聚合物與將上述單體成分、聚合溶劑、聚合起始劑、 視需要的鏈轉移劑一次性地加入至聚合裝置中的方法相 比，添加入共聚合物中的單體單元的偏差小、且單體單元 連續地排列而成的鏈的比例小’因此對於抗蝕溶劑的溶解 性、抗#圖案側壁的平坦性優異。 馨但是，於上述專利文獻2、專利文獻3所記載的方法 中’存在微影製程用共聚合物的溶解性、或抗蝕劑組成物 的感光度未得到充分改善的情況。 於利用微影製程的圖案形成的微細化進一步發展的過 程中，有想要使用單體單元（同一種類的單體）連續地排 列而成的鏈的比例更小、及/或單體單元的組成比的偏差更 小、於工業上抗蝕劑感光度及/或解析度更高、對於抗蝕溶 劑的溶解性比先前更優異的抗蝕劑用共聚合物的期望。 201222146 •---- ΛΓ 通常，於藉由核磁共振（Nuclear Magnetic Resonance， NMR)法、紅外吸收（lnfrared，IR)法等分光化學分析法， 熱解氣相層析法（Pyrolysis-Gas Chromatography，PyGC) 法專分離分析法’或質譜分析（Mass Spectrometry，MS) 法所獲得的信號中’針對各個因子找出特徵性的信號，並 根據其彳§號強度而算出共聚合物的鏈結構（例如，參照非 專利文獻1)。 但是 伴Ik共聚合物的構成單元的數量變多，或者即 便構成單元的數量少，因各成分的特徵性的信號重曼等， 而存2法根據測定結果明確地分離所獲得的信號的情 :者於二櫨ϊί藉由測定所獲得的資料的分析需要時間、 =3齡躲果賴㈣定量_準辦方面精度不 π取合物的，Claim priority ' and refer to its contents in this case. [Prior Art] In general, in order to measure the properties of a polymer, particularly a copolymer, in-line in a polymerization reactor system, and to control the polymerization reaction, it is necessary to analyze the measured properties of the polymers. For example, it is conceivable to evaluate the characteristics of a resist (a resist, and a product) which is one type of a copolymer, which is a composition for a lithography process used in the manufacturing process of a semiconductor element. Things. In the manufacturing steps of semiconductor elements, liquid crystal elements, and the like, in recent years, the micro-shadowing system has been rapidly developed. As the micro-E method '*_, the short micro-denier of the irradiation light irradiated on the opposite side is formed. In the study, the excimer laser (wavelength: 248 nm) ArF excimer is being researched to seek further progress. Short-wavelength molecular f-wavelength: 2: W η") lithography process technology and EUV quasi-n 13·5ηηι) lithography process technology. As a resist composition which can preferably correspond to the shortening of the irradiation light and the refinement of the 5 201222146 pattern, a polymer containing acid desorption and being desorbed by the action of an acid to form an alkali-soluble polymer, and light have been proposed. The acid-amplified anti-composition of the acid-producing m-gas is undergoing development and improvement of the composition. 2. As a chemical polymer for anti-money agents used in the ArF excimer laser lithography process, it is attracting attention for a thin acid polymer which is transparent to light having a wavelength of 193 nm. The acrylic polymer is bonded with (A) an ester having a alicyclic hydrocarbon group having a lactone ring, and (B) an ester having a group detachable by an action of an acid (曱) a copolymer of a acrylate, and a (c) ester-bonded hydrocarbon group having a polar substituent or a heterocyclic group containing an oxygen atom (a methyl acrylate) as a resist for a resist It has been described (for example, refer to Patent Document 1). However, a polymer of (mercapto) acrylate is usually polymerized by a radical polymerization method. The earthworm 〇 usually has a diversity of two or more kinds of monomers. In the polymer, the copolymerization reactivity ratio between the monomers is different, so the copolymerization ratio of the polymer formed in the initial stage of polymerization and the later stage of polymerization is different, and the obtained polymer becomes a composition distribution. When there is a variation in the composition ratio of the monomer unit in the product, the solubility in a solvent tends to be low, and when the resist composition is prepared, it takes a long time or insoluble matter to be dissolved in the solvent, so that there is a build-up The number of steps is increased, etc. In addition, the sensitivity of the obtained resist composition is likely to be insufficient. In addition, in the multicomponent polymer, the regularity of the chain corresponds to each monomer. The copolymerization reactivity is different. There are many monomer units which are continuous and arranged, and the conjugated polymer tends to lower the side resistance. Therefore, it is sought to reduce the chain of the monomer units continuously arranged. Copolymers. For the purpose of these problems, for example, in order to obtain a resist having a high resolution, a monomer having a relatively fast polymerization rate and a relatively slow monomer are called for the first step and the latter step. A method of synthesizing a copolymer having a narrow distribution of a copolymer (for example, refer to Patent Document 2 and Document 3). A copolymer for a resist produced by the methods of Patent Document 2 and Patent Document 3 and The monomer unit, the polymerization solvent, the polymerization initiator, and the optional chain transfer agent are added to the polymerization device at a time, and the variation of the monomer unit added to the copolymer is small, and The ratio of the chain in which the unit cells are continuously arranged is small. Therefore, the solubility in the resist solvent and the flatness of the side wall of the pattern are excellent. However, in the methods described in Patent Document 2 and Patent Document 3, the present invention exists. The solubility of the copolymer for the lithography process or the sensitivity of the resist composition is not sufficiently improved. In the process of further development of the pattern formation by the lithography process, it is desirable to use a monomer. The ratio of the units in which the units (the same type of monomers) are continuously arranged is smaller, and/or the variation in the composition ratio of the monomer units is smaller, and the sensitivity and/or resolution of the resist are higher in the industry. The solubility of the resist solvent is better than that of the resist copolymer for the resist. 201222146 •---- ΛΓ Generally, by Nuclear Magnetic Resonance (NMR), infrared absorption (Infrared, IR) aliquot photochemical analysis, pyrolysis-gas Chromatography (PyGC) method separation analysis method or mass spectrometry (MS) method In the middle, a characteristic signal is found for each factor, and the chain structure of the copolymer is calculated based on the intensity of the 彳§ (for example, refer to Non-Patent Document 1). However, the number of constituent units associated with the Ik copolymer is increased, or even if the number of constituent units is small, the characteristic signal of each component is heavy, and the method of clearly separating the obtained signals according to the measurement result is used. : The analysis of the data obtained by the measurement in the second 栌ϊ ί requires time, = 3 years old to hide the fruit (4) Quantitative _ the accuracy of the standard is not π,

效地使用所獲得的結果的情況。 ，，M 用，該方法是應4 1用法的分析得到有效利 (Che_etrics )的1 :::或化學計量學 量的最大化為目標圖等化學資料所獲得的化學資訊 分子材料的方法、或'〜例如有根據近紅外光譜識別高 獻4及專利文獻5)。弋雄度的方法（例如，參照專利文 [先如技術文獻] [專利文獻] 201222146 HUZdopif 丨f利文=1]曰本專利特開2〇〇2 145955號公報 [專利文獻2]日本專利特開雇〗·麗56號公報 [專利文獻3]日本專利特開昭57-1湖1號公報 [專利文獻4]日本專利特開細29⑽9號公報 [專利文獻5]日本專利特開2⑻2_遍9 [非專利文獻] m [非專利文獻1]新版高分子 化學會高分子分析研究懇1 日本分析 〜、P.233〜、ρ·69:;》4會編’紀伊國屋書店，P⑽ 【發明内容】 若使用上述專利文獻4及專利文獻5的分析的方法， 則無⑥為了評價抗_用絲合物， 抗姓劑料聚合難其他添加物來製備抗的 ϋΐ抗=用組成物（實際使用的抗賴）照射光來進 灯顯影’然後進行抗钮劑的特性評價。 如此，專利文獻4及專利文獻5各自的分析方法 所製造的抗_用共聚合物的性能進行評價，不僅 而且可排除抗姉m絲合細相齡的因此， 可有效地用崎價抗剌㈣共聚合物本身 成物時的触（包轉糾的柄感光歧顯料 溶劑的溶解度等的微影製程特性）。 、 另外’於製造積體電路時的微影製程步驟中， 成如下的薄臈的韻_組綱^外的微難_ 的評價亦與抗侧敎成物_重要，料膜是形成$ 201222146 導體材料上所塗佈的抗蝕劑用組成物的上層或下層的抗反 射膜、間隙填充膜、面塗膜等薄膜。 ，，於含有微影製程用共聚合物的微影製程用組成物 中疋否具有用以進行高精度的微細加工的特性（微影製 程特性）頗為重要。 該微影製程用組成物亦必需與評價抗#劑用組成物的 情況同樣地，即便不實際進行利用使用微影製程用共聚合 物所製備的微影製程用組成物的微影製程步驟，亦可坪價 將該微影製糊共聚合物祕微難程驗成 微影 製程特性。 抗反射膜疋形成於抗触劑用組成物的膜的下層，用於 抑制來自半導體材料的光的反射而提昇抗蝴用組成物的 曝光的精度的微影製程用組成物。另外，間隙 成於抗敍劑用組成物的膜的下層，用於將二 凸平坦化而提昇抗蝕劑用組成物的曝光精度的微影製程用 組成物。另外，面塗膜是形成於抗蝕劑用組成物的膜的上 層，用於保護抗蝕劑用組成物的表面的微影製程用组成 物。該些抗反射膜、間隙填充膜、面塗膜是用於提昇製造 積體電路時的構成微影製程的曝光的精度所必需的構造， 且是積體電路的微細化所不可或缺者。 但是，於專利文獻4、專利文獻5及非專利文獻i等 中，因使用PyGC法（熱解氣相層析法）推斷組成的定量， 故由於熱解效率根據共聚合物中所含有的單體單元的種類 而不同、或無蚊量祕得反映單體單元的熱解產物等原 201222146 HUZOdpif 因，因此有時於實用方面產生必需使用校正係數或三維繪 圖等問題。 本發明是鑒於上述課題而完成的發明，其目的在於解 決下述（1)〜下述（5)中的1個以上。 (1)提供^種可提昇對於溶_溶解性、及用於抗蚀 劑組成物時的感光度的微影製程用共聚合物共聚合物。The situation in which the results obtained are used effectively. ,,M, the method is a method for obtaining a chemical information molecular material obtained by chemical analysis of a target image or the like by using a 1:1:: or a stoichiometric amount of the effective profit (Che_etrics), or '~ For example, there is a recognition based on near-infrared spectroscopy 4 and Patent Document 5).方法 度 的 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 =1 Japanese Patent Laid-Open No. SHO 57-1 No. 1 (Patent Document 4) Japanese Patent Laid-Open Publication No. Hei 29 (10) No. 9 (Patent Document 5) Japanese Patent Laid-Open No. 2 (8) 2 [Non-Patent Document] m [Non-Patent Document 1] New Polymer Chemical Society Polymer Analysis Study 日本 1 Japanese Analysis ~, P.233~, ρ·69:; 4" will edit 'Kiyokuya Bookstore, P(10) [Summary of the Invention] When the method of analysis of the above-mentioned Patent Document 4 and Patent Document 5 is used, there is no 6 in order to evaluate the anti-filament compound, and it is difficult to polymerize other additives in the anti-surname agent to prepare an anti-antibody composition (actually used) The illuminating light is used for the development of the lamp. Then, the characteristics of the anti-button agent are evaluated. Thus, the performance of the anti-co-polymer produced by the analysis methods of each of Patent Document 4 and Patent Document 5 is evaluated, not only and can be excluded. Because of the age of the anti-mite m silk, there may be Effectively use the anti-cryogenic anti-mite (4) thief process characteristics when the co-polymer itself is formed into a substance (the lithography process characteristics such as the solubility of the solvent of the sensitization solvent). In addition, the lithography when manufacturing the integrated circuit In the process steps, the evaluation of the following 的 韵 组 组 组 组 组 外 外 外 外 外 的 的 的 的 的 的 的 的 的 的 的 的 , , , , , , , , , , , , , , , , , , , , , , , A film such as an anti-reflection film, a gap-fill film, or a top coat film of an upper layer or a lower layer of a material, and a fine-grained process for a high-precision microfabrication in a composition for a lithography process containing a eutectic copolymer. The characteristics of the lithography process are important. The composition for the lithography process must be prepared in the same manner as in the case of evaluating the composition for the anti-agent, even if it is not actually used by using a copolymer for lithography. The lithography process step of the composition for the lithography process can also be used to determine the lithography process characteristics of the lithographic paste copolymer copolymer. The antireflective film is formed on the film of the composition for anti-contact agent. Lower layer for suppressing semiconductors A composition for a lithography process which enhances the precision of exposure of the composition for the anti-bushing composition by the reflection of the light of the material. Further, the gap is formed in the lower layer of the film for the composition for the anti-synthesis agent, and is used for flattening the two convexities to enhance the resistance. The lithography process composition for the exposure precision of the composition for the etchant. The top coat film is formed on the upper layer of the film for the resist composition, and is used for the lithography process for protecting the surface of the resist composition. The antireflection film, the gap-fill film, and the top coat film are necessary for improving the precision of the exposure of the lithography process when manufacturing the integrated circuit, and are not necessary for miniaturization of the integrated circuit. However, in Patent Document 4, Patent Document 5, and Non-Patent Document i, etc., since the quantification of the composition is estimated by the PyGC method (pyrolysis gas chromatography), the pyrolysis efficiency is based on the copolymer. The type of the monomer unit to be contained differs, or the amount of the mosquito-free substance reflects the original 201222146 HUZOdpif factor such as the pyrolysis product of the monomer unit. Therefore, problems such as correction coefficient or three-dimensional drawing are sometimes required in practical use. The present invention has been made in view of the above-described problems, and an object of the invention is to solve one or more of the following (1) to (5). (1) A eutectic copolymer for a lithography process which improves the solubility of a solvent and a resist for a resist composition.

⑵提供-種可改善絲合物巾的單财元的含有比 率的偏差’可提#對於賴的轉性、及用於抗鋪組成 物時的感光度的微影製程用共聚合物及其製造方法。 、（3)提供-種使用上述微影製刻共聚合物的抗姓劑 組成物、及使用該抗_組成物製造形成有圖案的基板的 的共地評價共聚合物的共聚合物鏈結構 共丄共聚合物的單體單元的排列狀態的 決。上述目的是U由下述的^〜^〉的本發明來解 體a i〜種，影製程用共聚合物’其是使2種以上的單 別自該;L單t2以上的整數)聚合而成、且包含分 心的微難抑的單料〜單體單元 組價方法所算出的單體單元的三單元 的口松共聚合物中為2〇莫耳％以下，上述共聚合 11 201222146 物的評價方法是經過下述（I)〜下述（Ιν)的過程，算出 表示包含多個單醴單元的共聚合物中的同一種類的上述單 體單元的三單元縝（triad)於整個組成中所佔的比例的三 單元組分率。 (I)目標變數分析過程，根據上述單體單元的此聚人 反應性比，_下述計算式（H)算㈣為已知樣^二 聚合物的組成中的同一種類的單體單元的三單元組八八 (Π)說_數分析過程，_上述已知樣品二_ 合物的NMR ;収巾的化#_量及錢強度而輸出說明 藉由部分最小平方回歸而 數的回歸模型的回歸式， 求出 生成 (III)模型生成過程， 上述目標變數與上述說明變 回歸模型的係數。 (IV)樣品分析過程，使用上述㈣模型 =i=R測定中的化學位移量與信號強ί ^率 同—種_單體單元的上述三軍元 陳1](2) Providing a lithographic process copolymer for improving the ratio of the content of the single-finance of the silk-skin towel, and the lithography process for the susceptibility to the anti-sand composition Production method. (3) providing an anti-surname composition using the above-described lithography-imprinted copolymer, and a copolymer-common copolymer chain structure of the co-evaluated copolymer produced by using the anti-composition to form a patterned substrate The arrangement of the monomer units of the conjugated co-polymer is determined. The above object is that the U is disintegrated from the following invention by the following method, and the copolymer for the process process is obtained by polymerizing two or more kinds of monomers from the above; And the mono-unit cell group valence method including the distracting unit is a monomer unit group method, and the monomer unit of the unit cell has a molar ratio of 2 〇 mol% or less, and the above-mentioned copolymerization 11 201222146 In the evaluation method, a tri-unit triad representing the same type of the monomer unit in the copolymer containing a plurality of monofluorene units is calculated through the following processes (I) to (下述ν); The proportion of the three-unit component of the proportion. (I) target variable analysis process, according to the above-mentioned monomer unit reactivity ratio, _ the following calculation formula (H) (4) is the same type of monomer unit in the composition of the known polymer The ternary group VIII (Π) says the _ number analysis process, _ NMR of the above known sample bis compound; the aging amount of the towel and the strength of the money, and the output shows the regression model by partial least squares regression The regression equation is used to find the generator (III) model generation process, and the above-mentioned target variables are the coefficients of the variable regression model described above. (IV) Sample analysis process, using the above (4) model = i=R determination of the chemical shift amount and the signal strength ί ^ rate same as the kind _ monomer unit of the above three military yuan Chen 1]

(Η) P(j j j) (%) = 1 Ο ο χ [Μ&gt; Ρη=^- f[Mh) A=1 rjh (陶是絲合物中的單體單元」·的莫耳分率，於草 201222146 s-uzoopif 體單元j為共聚合物的成長末端的單體單元時，Pjj是與單 體（單元）j進行反應的概率，[Mj]及[Mh]是反應系統中的 各單體單元j、h的莫耳分率，rjh是自單體（單元）』至單 體（早元）h的共聚合反應性比）。 &lt;2&gt; —種微影製程用聚合物的製造方法，其是包括一 邊向反應益内滴加早體及聚合起始劑，一邊於該反應器内 使2種以上的單體αι〜單體αη (其中，n表示2以上的整 數）進行聚合’而獲得包含單體單元a'i〜單體單元α'η (其 中，α·ι〜α’η表示分別自單體αι〜單體〜衍生出的單體單 元）的聚合物（P)的聚合步驟的微影製程用聚合物的製 造方法， 其使用含有單體的溶液Sa (a為1〜d，d為1以上的 整數）、溶液Tb (b為1〜e，e為1以上的整數）及溶液 Uc (c為1〜f ’ f為1以上的整數）， 上述聚合步驟具有分別向反應器内供給溶液sa及溶 液Tb的主步驟、及於該主步驟結束後將溶液Uc供給至反 應器内的後步驟， 上述主步驟中’於向上述反應器内滴加上述聚合起始 劑之前、或與開始滴加該聚合起始劑的同時，向該反應器 内開始供給以第1組成含有上述單體αι〜單體αη的溶液 Sa， 於向該反應器内開始供給上述溶液Sa之後、或與開始 供給該溶液Sa的同時’向該反應器内開始滴加以第2組成 含有上述單體A〜單體αη的溶液7¾，且溶液Sa的供給於 13 201222146 溶液Tb的滴加結束之前結束， _當表示欲獲得的聚合物（P)中的單體單元…〜單體 單元％的含有比率的目標組成（單位：莫耳％)為（X，！： α’2 ...··· 0t’n 時， 組成=:=，〜溶液&quot;各自的單體的組成的第2 上述’谷液Sl〜溶液Sd各自的單體的組成與目標組成 不同、’ 該溶液S1〜溶液Sd的合計的單體的組成的第 且成疋單體％〜單體％之巾，共聚合反應速度最慢的單 體的比例$於目標組成的組成， ^上述溶液171〜溶液各自的單體的組成與目標組成 ^^，，轉⑺〜溶液陶合計的單體的組成的第 體αΐ〜賴〜之巾，料合反應速度最慢的單 體的比例少於目標組成的組成。 α’2 α’η時 半上-述&lt;2&gt;所述之微影製程用聚合物的製造方 1，二中當表示欲獲得的聚合物（p)中的單體單元吣〜 單體單元α，η的含有比率的目標組成（單位：莫耳％)為α,1: 作為上述溶液S1〜溶液Sd的合計的單體的組成的第 1組成的各單體單元的含有比率分別為藉由下述方法（1) 〜方法（4)所求出的s，a中的各單體單元的含有比率的值 的0.8倍〜1.2倍的範圍内， 士述溶液U1〜溶液uf的合計所含有的單體的合計量 為總單體供給量的0.1質量％〜10質量％。 201222146 wzoopif 、f曰辨&quot;、，岐的滴加速度，將含有單體組成盘上 述目=成α1: α，2:: α、相同的 質士 的反廍⑽二ί 溶液滴加至僅加入有溶劑 ’當自滴加開始算起的經過時間為ti、切 W ϋ殘反應器内的賴α1〜單體％的組成 早耳%)Μ1:Μ2:..·:Μη，及自…為止的： 2 t為止的顧、·时财成⑽ 體早4〜單體單元α，η_率（單位：莫耳％)p丨·ρ2:和 f η 0 α，.（.）找j 述&amp; · &amp; . ··. : Ρη最接近目標組成α·ι : 上2的整數L ^至^1為止的期間U為1以 根據該自^至一為止的期間」内的P1:P2: · 二Ϊ=夺間‘内的^:...:虬的值，藉由 莫耳。/(、4)右以αη.α12:…·α1η表示s,a的組成（單位： ^耳/°)，以F1、F2、·；表示上述⑶中所求出的因數， 則 ttll=avFm㈣…、·_.α1η”,Λ。 的製ί 上甘述^^或^所述之微影製程用聚合物 ,，/、中當表示欲獲得的聚合物（Ρ)中的單體 〜早體單元α’』含有比率的目標組成（單位：莫 斗/〇)為 a'】：α·2 : . : α,η 時， 、 乍為上述办液U1〜溶液uf的合計的單體的組成的第 15 201222146 •tVAUOpil 3組成的各單體單元的含有比率分別為藉由下述方法（5) 〜方法（8)所求出的u’c中的各單體單元的含有比率的值 的〇·8倍〜1.2倍的範圍内。 (5)以固疋的滴加速度’將含有單體組成與上述目標 組成a’i : α’2 :…：α’η相同的單體混合物1〇〇質量份、聚 合起始劑、及溶劑的滴加溶液滴加至僅加入有溶劑的反應 器内，當自滴加開始算起的經過時間為t】、bb時，长 j分別殘存於反應器内的單體αι〜單體％的組成（單位： 莫耳％) M〗：M2 : : Mn，及自…2為止的期間、自 的期間、...内分別生成的聚合物中的單體單元 1早體早凡αη的比率（單位：莫耳％) Pi : p 2· ... . αη的時段自^至Wi為止 上的整數）」。 』马1以 ⑺根據該「自tjtm+i為止的期間」内的：. =值、及經過時間tm内的Mi: m2 ··...:砍的值，择由 下述式而求出因數Fl、F2、...VF = = Pn/Mn。 2 ^2/M2'...Fn 莫耳其的⑽ ，為〇)表示上述⑺中所求出的因數Fn:ft小者替 (a'^Fj+ a'2xF2+. + a'xV Λ 31 —叫邛】/ &amp;f2+ +a，xF) n n)、a32 = a2XF2/“W1 + ct，nxFn)e &quot; V^aixFi + a'2xF2-f..&gt; + 201222146 4U2»»pif &lt;5&gt;—種微影製程用聚合物，其藉由如上述&lt;2&gt;所 述之製造方法而獲得。 &lt;6&gt;—種抗蝕劑組成物，其含有如上述&lt;!&gt;或&lt;5 &gt;所述之微影製则聚合物、及藉由光化射線或放射線的 照射而產生酸的化合物。(Η) P(jjj) (%) = 1 Ο ο χ [Μ&gt; Ρη=^- f[Mh) A=1 rjh (Tao is a monomer unit in the filament) · Mohr fraction, Grass 201222146 s-uzoopif When the unit cell j is a monomer unit at the growth end of the copolymer, Pjj is the probability of reacting with the monomer (unit) j, and [Mj] and [Mh] are the monomers in the reaction system. The molar fraction of units j and h, rjh is the copolymerization reactivity ratio from monomer (unit) to monomer (early element) h). &lt;2&gt; A method for producing a lithographic process polymer comprising adding two or more monomers α1 to a single unit in the reactor while adding an early body and a polymerization initiator to the reaction The body αη (where n represents an integer of 2 or more) is polymerized' to obtain a monomer unit a'i to a monomer unit α'η (where α·ι~α'η represents a monomer from the monomer α1~ a method for producing a polymer for lithography process in a polymerization step of a polymer (P) derived from a monomer unit (P), which uses a solution Sa containing a monomer (a is 1 to d, and d is an integer of 1 or more) And a solution Tb (b is 1 to e, e is an integer of 1 or more) and a solution Uc (c is an integer of 1 or more and 1 'f' is 1 or more), and the polymerization step has a solution sa and a solution Tb supplied to the reactor, respectively. a main step, and a subsequent step of supplying the solution Uc to the reactor after the completion of the main step, in the main step, 'before dropping the polymerization initiator into the reactor, or starting to add the polymerization Simultaneously with the starter, the supply to the reactor begins with the first component containing the monomer αι~ The solution Sa of the body α η starts to supply the solution Sa in the reactor, or starts to supply the solution Sa, and begins to drip the second composition containing the monomer A to the monomer α η into the reactor. Solution 73⁄4, and the supply of the solution Sa is completed before the end of the dropwise addition of the solution Tb of 13 201222146, _ when indicating the target composition of the content ratio of the monomer unit ... to the monomer unit % of the polymer (P) to be obtained (unit) : Moer %) is (X,!: α'2 ...··· 0t'n, composition =:=, ~solution&quot; the composition of the respective monomers of the second above 'Valley Sl~ solution The composition of each monomer of Sd is different from the target composition, and the composition of the monomer of the total of the solution S1 to the solution Sd is the first and the monomer % to the monomer %, and the monomer having the slowest copolymerization reaction rate. The ratio of the composition of the target composition to the composition of the composition of the above solution 171 ~ solution of the respective monomer composition with the target composition ^ ^,, transfer (7) ~ solution of the total composition of the monomer of the body of the body α ΐ ~ Lai ~ towel, material The proportion of monomers with the slowest reaction rate is less than the composition of the target composition. 2 α'η时半半- <2> The preparation of the lithography process polymer 1 and 2, when the monomer unit 吣~ monomer unit α in the polymer (p) to be obtained is represented The target composition (unit: mole %) of the content ratio of η is α, and the content ratio of each monomer unit of the first composition which is a composition of the total of the above-mentioned solutions S1 to Sd is In the range of 0.8 times to 1.2 times the value of the content ratio of each monomer unit in s, a obtained by the following methods (1) to (4), the total of the solution U1 to solution uf is contained. The total amount of the monomers is from 0.1% by mass to 10% by mass based on the total monomer supply amount. 201222146 wzoopif, f曰“,, 岐, the drip acceleration, will contain the monomer composition disk above the target = α1: α, 2:: α, the same quality of the 廍 廍 (10) There is a solvent 'the elapsed time from the start of the dropwise addition is ti, the composition of the lag α1 ~ monomer % in the residual W ϋ residual reactor is %) Μ1: Μ2:..·: Μη, and since : 2 t until Gu Shi·Cai Cai Cheng (10) Body early 4~ monomer unit α, η_ rate (unit: mole %) p丨·ρ2: and f η 0 α,.(.) find j &amp;; · · · · : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : · The value of ^:...:虬 in the second Ϊ 夺 夺 , 藉 , , , , , , , 莫 莫 莫 莫/(,4) Right represents αη.α12:...·α1η represents the composition of s,a (unit: ^ ear/°), and F1, F2, ·; represents the factor obtained in (3) above, then ttll=avFm (4) ...,·_.α1η", Λ. The lithographic process polymer described in ^^ or ^, /, when the monomer in the polymer (Ρ) to be obtained ~ early The body unit α' contains the target composition of the ratio (unit: Modou/〇) as a']: α·2 : . : α, η, 乍 is the total monomer of the above-mentioned liquid U1 to solution uf The content ratio of each monomer unit of the composition of the 15th 201222146 • tVAUOpil 3 composition is the value of the content ratio of each monomer unit in u'c obtained by the following methods (5) to (8). In the range of 8 times to 1.2 times. (5) The monomer mixture having the same monomer composition as the above-mentioned target composition a'i : α'2 :...:α'η The dropwise addition solution of the hydrazine mass, the polymerization initiator, and the solvent is added dropwise to the reactor in which only the solvent is added. When the elapsed time from the start of the dropwise addition is t] and bb, the length j remains in the residue. reaction The composition of the monomer α1 to monomer % in the monomer (unit: mol%) M: M2: : Mn, and the list of the polymers generated in the period from ..., the period, and the ... The ratio of the body unit 1 to the early α α (unit: mole %) Pi : p 2· ... . The period of αη from ^ to the integer above Wi). "Ma" 1 is obtained by (7) based on the value of .: = in the "period from tjtm+i" and the value of Mi: m2 ··...: cut in the elapsed time tm. The factors Fl, F2, ... VF = = Pn / Mn. 2 ^2/M2'...Fn Moth's (10), 〇) indicates the factor Fn: ft found in (7) above (a'^Fj+ a'2xF2+. + a'xV Λ 31 —邛] / &amp;f2+ +a,xF) nn), a32 = a2XF2/"W1 + ct,nxFn)e &quot; V^aixFi + a'2xF2-f..&gt; + 201222146 4U2»»pif &lt;5&gt; A lithographic process polymer obtained by the production method according to the above &lt;2&gt;. &lt;6&gt; - a resist composition containing the above &lt;!&gt;&lt;5&gt; The lithographic polymer described above, and a compound which generates an acid by irradiation with actinic rays or radiation.

一禋形成有圖案的基板的製造方法，其包括：將 如上述&lt; 6j&gt;所述之抗蝕劑組成物塗佈於基板的被加工面 上而形成抗蝕膜的步驟；對該抗蝕臈進行曝光的步驟；以 及使用顯驗對經曝光的祕騎行顯f彡的步驟。 &lt;8&gt;f種共聚合物的評價方法，其是算出表示包含2 ，以亡的單體單元的絲合物的㈣巾的同-麵的上述 單體單元的三單元組於整她成巾所佔的_的 分率的共聚合物的評價方法，其包括： 、、' -目標分㈣程，目標魏分析部娜±述單 兀的共聚合反應性比，下述計算式（H)算出作 知樣品的共聚合物的組成中的同—種_單體單元的^ 元組分率； 平 。說明變數分析過程，說明變數分析部根據上述已 的共聚合㈣NMR狀巾雜學轉量及信 品 輸出說明變數； °〜強度而 、模型生成過程，模型生成部藉由部分最小平 求出上述目標變數與上述說明變數的回歸模型的^， 生成上述回歸模型的係數；以及 式’ 樣品分析過程，樣品分析部使用上述回歸模型，根據 17 201222146 未知樣品共聚合物的NMR測定中的化學位移量與信號強 度，算出未知樣品中的同一種類的單體單元的上述三 組分率。 —平70 [數2] ^ t j j j } (%) = 1 〇 〇 χ [ινι, ] χ ρ . , χ ρ ··，） f[Mh) rjh 时是共聚合物中的單體單元』的莫耳分率，於 體早7為共聚合物的成長末端的單體單元時，&amp;是與單 j進行反應的概率，及陳反應丄統中的 早⑴、h的莫耳分率、是自單體（單元）』至單 體（早兀）h的共聚合反應性比）。 中的種共聚合她齡㈣法，妓分析共聚合物 =的早體早元㈣舰態的共聚合物組成分析方法，其包 2定·提取過程，败:㈣提取部自上述共聚合物 ^繼_ ’將包讀成上料聚合㈣上料 的波長的範_NMR賴作為絲合物啦㈣而提取. nii分分析過程i域分分析部進行對於上述共聚合 及疋轉、及上料體各自的NMR光譜的單體 t化=斜光顧度社成分分析，直謂應於上述 早體的數量n(n為2以上的整數）的第η主成分為止； 201222146 距離算出過程，數值轉換部求出上述第l主成分至第 11主成为的主成分軸所構成的β維的主成分空間中，自包 3所有上述主成分軸中的上述單體的主成分得分所表示的 f標點的n-i維的比較空間，至上述共聚合物的主成分得 y 刀所表示的對象座標點為止的評價距離；以及 、特性評價過程，特性評價部藉由上述評價距離而評價 上述共聚合物的特性。A method for producing a substrate on which a pattern is formed, comprising: a step of applying a resist composition as described in the above &lt;6j&gt; to a surface to be processed of a substrate to form a resist film;臈 the step of performing exposure; and the step of using the display to show the exposure of the exposed secret. &lt;8&gt; A method for evaluating a f-type copolymer, which is to calculate a triad of the above-mentioned monomer unit which represents the same side of the (4) towel containing the dead monomer unit, and The evaluation method of the copolymer of the fraction of _ of the towel, which includes: , '-target fraction (four), the ratio of the copolymerization reactivity of the target Wei analysis section Na, the following calculation formula (H) Calculate the ratio of the constituents of the same type of monomer in the composition of the copolymer of the known sample; The variable analysis process will be described, and the variable analysis unit will explain the variables according to the above-mentioned copolymerization (4) NMR-like towel transfer amount and the letter output; °~ intensity, model generation process, and the model generation unit obtains the above target by partial least square The coefficient of the regression model of the variable described above is generated, and the coefficient of the regression model is generated; and the sample analysis process, the sample analysis section uses the above regression model, according to the chemical shift amount in the NMR measurement of the unknown sample copolymer of 17 201222146 and Signal intensity, the above three component ratios of the same type of monomer units in the unknown sample were calculated. —平70 [数2] ^ tjjj } (%) = 1 〇〇χ [ινι, ] χ ρ . , χ ρ ··,) f[Mh) rjh is the monomer unit in the copolymer Ear fraction, when the body 7 is a monomer unit at the growth end of the copolymer, &amp; is the probability of reacting with a single j, and the early (1), h molar fraction in the Chen reaction system, The ratio of copolymerization reactivity from monomer (unit) to monomer (early 兀) h). The method of co-polymerization of her age (four) method, 妓 analysis of co-polymer = early body early element (four) ship state copolymer composition analysis method, its package 2 · extraction process, defeat: (4) extraction part from the above copolymer ^ Following _ 'read the package as the loading of the polymerization (4) the wavelength of the loading of the _NMR ray as a silk compound (4) and extract. Nii sub-analysis process i domain analysis section for the above-mentioned copolymerization and entanglement, and on The monomer NMR of the NMR spectrum of the material is analyzed according to the composition of the oblique light, and the value is n (n is an integer of 2 or more) of the η principal component of the above-mentioned early body; 201222146 Distance calculation process, numerical value The conversion unit obtains, in the principal component space of the β-dimension formed by the principal component axis of the first principal component to the eleventh main component, the f component represented by the principal component score of the monomer in all the principal component axes of the package 3 The evaluation space of the ni-dimensional of the punctuation, the evaluation distance from the target coordinate point indicated by the y-knife to the main component of the above-mentioned copolymer; and the characteristic evaluation process, the characteristic evaluation unit evaluates the above-mentioned copolymer by the above evaluation distance Characteristics.

j10&gt;—種共聚合物的製造方法，其包括：使2種以 上的單體進行聚合而獲得共聚合物的步m藉由如上 j &lt; 8 &gt;所述之絲合物的評價方法，騎獲得的共聚合物 進行評價的步驟。 μ ^U&gt;&quot;種共聚合物的製造方法，其包括：使2種以 的早體進行聚合祕得共聚合物的步驟；以及藉由如上 述之共聚合恤成分析方法，對賴得的共聚合 物進仃分析的步驟。 根，本發明，可獲得—種共聚合財的同—種類的單 二單元組分率降低、對於溶劑的溶解性良好、用 钮劑組成物時具有高感光度的微影製程用共聚合物。 根=本發明，可獲得一種單體單元的含有比率的偏 及刀子垔的偏差得到改善，對於溶劑的溶解性良好， 用於抗蝕劑組成物時具有高感光度的微影製程用共聚合 4勿。 、口 根據本發明’可獲得一種對於抗蝕溶劑的溶解性優 異、感光度優異的化學增幅螌的抗钮劑組成物。 201222146 根據本發明，可穩定地形成形成有高精度的微細的抗 I虫圖案的基板。 β根據本發明’可簡單地評價絲合物的絲合物鏈， 且可不實際生餘餘，崎獅該絲合物製成組成物 時的特性。 根據本發明’可簡便地推斷共聚合物的鏈結構的無規 性’且可不實際生成組成物，卿價將該共聚合物製成組 成物時的特性。J10&gt; - a method for producing a copolymer, comprising: a step of obtaining a copolymer by polymerizing two or more kinds of monomers to obtain a copolymer, and the method for evaluating a filament compound according to the above j &lt; 8 &gt; The step of evaluating the obtained copolymer was carried out. a method for producing a co-polymer, comprising: a step of polymerizing two kinds of precursors to obtain a copolymer; and using a copolymerization analysis method as described above The step of the co-polymerization analysis. According to the present invention, it is possible to obtain a copolymer of a lithographic process having a reduced rate of a single-unit component of the same type, a good solubility in a solvent, and a high sensitivity in a button composition. . Root = According to the present invention, it is possible to obtain a variation in the content ratio of the monomer unit and the deviation of the knives, and the solubility in a solvent is good, and the sensitization of the lithography process with high sensitivity for the resist composition is obtained. 4 Do not. According to the present invention, it is possible to obtain a chemically amplified ruthenium-resistant resist composition which is excellent in solubility in a resist solvent and excellent in sensitivity. According to the present invention, it is possible to stably form a substrate on which a fine anti-Iworm pattern with high precision is formed. According to the present invention, β can be simply evaluated, and the composition of the composition can be simply obtained without the actual residue. According to the present invention, the randomness of the chain structure of the copolymer can be easily inferred, and the composition can be formed without actually forming a composition.

因此’可簡便地評價共聚合物（祕劑用共聚合物、 U程用共聚合物）的組射，共聚合物中的單體的鍵 見丨生&quot;^可不實際使用共聚合物來製備組成物，而評 “有該絲合物的組成物（抗_賴成物、微影製程 用組成物）的特性。Therefore, the composition of the copolymer (the copolymer for the agent, the copolymer for the U-pass) can be easily evaluated, and the bond of the monomer in the copolymer can be found in the "co-polymer". The composition was prepared, and the characteristics of the composition (the composition for the anti-sludge, the lithography process) having the composition were evaluated.

，於&gt;、聚合物組成分析方法的實施形態中，使用專 =NMR /則疋所獲得的NMR光譜，求出主成分空間中，爸 2使用的所有單H的均聚物的座標闕嫌空間與則 私的共聚合物的座標點的距離即比較距離，並藉由該^ 又距離來判疋共聚合物的鏈結構中的單體的配置的無夫 ^ ’且根制無規絲進行使料聚合倾製備的組成4 、寺性評價’因此與先前相比可簡單地進行組成物的評價 另外，於絲合物喊分析枝的倾㈣中，當4 =。，巾的單體蚊量或鏈分布時因制定試樣的^ 加阿溫，故不存在如先前般由熱處理的溫度所; 的試樣的熱解效率的不同、或無法定_獲得反映構; 20 201222146 4U288pif 單元的熱解產物等測定料，此無“了校 此處，所謂無規性，是指鄰接的單體 狀態的特性，即是指鏈結構中，多個相同=== 結的嵌段少的鏈狀㈣雛。 早體4接並鍵 【實施方式】 元，=:趙= 單:的單是元^^ 成單元。另-方面，當僅表示為「單稱為構 聚合物前的單體。. 」^，表示成為共 於本說明書中，「（甲基)丙烯酸」表示丙 = :「(甲基赚氧基」表示丙雜氧基或?基:二 本說明書中的聚合物的重量平均分子量 ，分布（Mw/Mn)是藉由娜渗透層析法， 換鼻而求出的值。 、二4本乙烯 &lt;共聚合物（聚合物（P)) &gt; 本發明的實施形態中的共聚合物（以 聚合物（P))包含單體單元响〜單體單元α 稱為 〜α’η表示分別自單體αι〜單體％街生出二 αι 示2以上的整數）。 Μ早體早Ρη表 η的上限就容易獲得本發明的效果的觀點而^ , 為6以下。尤其於聚合物⑺為半導體微影^用= 21 201222146 合物（例如抗蝕劑用共聚合物）的情況下，更佳為5以下， 進而更佳為4以下。 例如，當時，聚合物（P)是包含單體單元α，广 單體單元α'2、單體單元α·3的三元系聚合物ρ(彡， 當n=4時，聚合物（p)是包含單體單元、單體單元以2、 單體單元α'3、單體單元α’4的四元系聚合物ρ (aVaVaVa、）。 聚合物（P)的用途並無特別限定。例如，較佳為微 影製程步驟中所使用的微影製程用共聚合物。作為微影製 程用共聚合物，可列舉··用於抗蝕臈的形成的抗蝕劑用共 聚合物，用於形成於抗蝕膜的上層的抗反射膜（τ〇ρ Anti-Reflective Coating，TARC)、或形成於抗蝕膜的下層 的抗反射膜（Bottom Anti-Reflective Coating，BARC)的 形成的抗反射膜用共聚合物，用於間隙填充膜的形成的間 隙填充膜用共聚合物，用於面塗膜的形成的面塗膜用共聚 合物。 微影製程用共聚合物的重量平均分子量（Mw)較佳 為I，000〜200,00〇,更佳為2,000〜40,000。分子量分布 (Mw/Mn)較佳為！.〇〜_，更佳為hl〜4〇。 聚合物（P)的單體單元並無特別限定，對應於用途 及要求特性而適宜選擇。 抑抗韻劑用共聚合物較佳為含有具有酸脫雜基的單體 單兀及具有極性基的單體單元，除^卜視需要亦可含 有公知的單體單元。 22 201222146 HUZOOpif 抗蝕劑用共聚合物的重量平均分子量（Mw)較佳為 I，000〜100,000，更佳為3,000〜30,000。分子量分布 (Mw/Mn)較佳為ΐ·〇〜3.〇，更佳為1 j〜2 5。 抗反射膜用共聚合物較佳為例如含有具有吸光性基的 單體單元，並且為了避免與抗蝕膜的混合，而含有具有可 與硬化劑等進行反應而硬化的胺基、醯胺基、羥基、環氧 基等反應性官能基的單體單元。 # 所謂吸光性基，是指對於抗蝕劑組成物中的感光成分 具有感光度的波長區域的光，具有高吸收性能的基，作為 具體例，可列舉具有蒽環、萘環、苯環、喹啉環、喹噁啉 %、噻唑環等環結構（亦可具有任意的取代基）的基。尤 其，當使用KrF雷射光作為照射光時，較佳為蒽環或具有 任意的取代基的蒽環，當使用ArF雷射光時，較佳為苯環 或具有任意的取代基的苯環。 作為上述任意的取代基，可列舉：酚性羥基、醇性羥 φ 基、羧基、羰基、酯基、胺基、或醯胺基等。 作為提供具有上述吸收性基的單體單元的單體的例 子，可列舉：笨乙烯、α_曱基苯乙烯、對甲基苯乙烯、對 沒基笨乙烯、間羥基苯乙烯等笨乙烯類及其衍生物 ，經取 代或未經取代的（曱基）丙烯酸笨酯、經取代或未經取代的 (曱基)丙烯酸萘酯、經取代或未經取代的（曱基)丙烯酸蒽曱 酯等具有乙烯性雙鍵的含芳香族的酯類等。 尤其’就良好的顯影性.高解析性的觀點而言，較佳為 具有經保護或未經保護的酚性羥基作為吸光性基的抗反射 23 201222146 膜用共聚合物。 作為具有上述吸光性基的單體單元.單體，例如可 (酉旨甲=丙烯酸节酉旨（實例的叫、（甲基)丙烯酸對經基苯 ⑽具吸f絲料料糾比浙财單體單元 (00莫耳/°)巾’較佳為10莫耳％〜100莫耳％。 λ! 的共聚合物較佳為例如具有用以流入至狹 射=:=黏度，並且為了避免與抗峨抗反 而含有具有可與硬化劑等進行反應而硬化的 反應性官能基的單體單元。 酸产列舉經基苯乙婦與笨乙稀、（甲基)丙烯 、（甲基基絲酯等單體的共聚合物。 子，中所使用的面塗膜用共聚合物的例 有取:含有具 〈單體單元.單體&gt; 對二(Ρ) ί使與其單體單元（〜單體單元Α分別 心：:二體較：聚/:獲得。單體較佳為具有 (甲基)两_醋對於波長行自由基聚合者。尤其’ 高。 曰対於/皮長25〇nm以下的曝光用光的透明性 使—體二=聚合物時適合 [具有酸脫離性基的單體單元.單體] 201222146 WZ66pif 抗截劑用共聚合物較佳為具有酸脫離性基。所謂「酸 脫離性基」，是指具有藉由酸而開裂的鍵的基，且是指藉由 ==Γ酸脫離性基的—部分或全部自聚合“ 於抗姓劑用組成财’含有具有酸脫離性基的單體單 兀的聚合物與酸成分進行反編可溶於驗性 可形成抗蝕圖案的作用。 ^ jIn the embodiment of the polymer composition analysis method, the NMR spectrum obtained by NMR / 疋 is used to determine the coordinates of all the H homopolymers used by Dad 2 in the main component space. The distance between the coordinates of the space and the private copolymer is the distance, and the distance between the space and the monomer in the chain structure of the copolymer is judged by the distance and the root is random. The composition 4 for the polymerization of the material was prepared, and the evaluation of the temple was carried out. Therefore, the evaluation of the composition can be easily performed as compared with the prior art. In addition, in the tilting (four) of the filament analysis branch, when 4 =. The individual mosquito amount or chain distribution of the towel is determined by the temperature of the sample, and there is no temperature of the heat treatment as in the previous case; the pyrolysis efficiency of the sample is different, or it is impossible to obtain the reflection structure. 20 201222146 4U288pif unit pyrolysis products and other materials, this is not here, the so-called random, refers to the characteristics of the adjacent monomer state, that is, in the chain structure, multiple identical === knot The block has fewer chained (four) chicks. The early body 4 joins the key [Embodiment] Yuan, =: Zhao = single: the single is the unit ^^ into the unit. Another-side, when only expressed as "single-called construction The monomer before the polymer.. ^, is indicated in the present specification, "(meth)acrylic acid" means C =: "(Methyl oxy group) means propenoxy or ketone: two instructions The weight average molecular weight of the polymer in the distribution (Mw/Mn) is a value obtained by changing the nose by Na-Permeation Chromatography. Two or four vinyls &lt;copolymer (polymer(P)) &gt The copolymer (in the polymer (P)) according to the embodiment of the present invention contains a monomer unit ringing ~ monomer unit α is referred to as ~α'η, respectively % Monomer αι~ Street monomers shown integer of 2 or more to give birth to two αι). The upper limit of the η early table η is easy to obtain the effect of the present invention, and is 6 or less. In particular, when the polymer (7) is a semiconductor lithography = 21 201222146 (for example, a copolymer for a resist), it is more preferably 5 or less, still more preferably 4 or less. For example, at the time, the polymer (P) was a ternary polymer ρ containing a monomer unit α, a wide monomer unit α'2, and a monomer unit α·3 (彡, when n=4, a polymer (p) The quaternary polymer ρ (aVaVaVa) containing a monomer unit, a monomer unit of 2, a monomer unit α'3, and a monomer unit α'4. The use of the polymer (P) is not particularly limited. For example, a copolymer for lithography process used in the lithography process step is preferred. Examples of the copolymer for lithography process include a copolymer for resist used for forming resist. Anti-reflection film (TARC) formed on the upper layer of the resist film or anti-reflective film (BARC) formed on the lower layer of the resist film a copolymer for a reflective film, a copolymer for a gap-fill film for forming a gap-filled film, a copolymer for a top coat for forming a top coat film, and a weight average molecular weight of a copolymer for a lithography process (Mw) is preferably from 1,000 to 200,00 Torr, more preferably from 2,000 to 40,000. The molecular weight distribution (Mw/Mn) is preferably 〇~_, more preferably hl~4〇. The monomer unit of the polymer (P) is not particularly limited, and is appropriately selected depending on the use and required characteristics. The copolymer for suppressing rhyme is preferably contained. The monomer monoterpene having an acid dedoping group and the monomer unit having a polar group may contain a known monomer unit as needed. 22 201222146 HUZOOpif Weight average molecular weight (Mw) of the copolymer for resist It is preferably from 1,000 to 100,000, more preferably from 3,000 to 30,000. The molecular weight distribution (Mw/Mn) is preferably ΐ·〇~3.〇, more preferably 1 j to 2 5. Antireflective film copolymer It is preferable to contain, for example, a monomer unit having a light-absorbing group, and to contain an amine group, a mercapto group, a hydroxyl group, an epoxy group, or the like which can be cured by reaction with a curing agent or the like in order to avoid mixing with the resist film. The monomer unit of the reactive functional group. The term "absorbent group" refers to a light having a high absorption property in light in a wavelength region having sensitivity to a photosensitive component in a resist composition, and specific examples thereof include Anthracene ring, naphthalene ring, benzene ring, quinoline ring, quinoxaline%, a group having a ring structure such as an azole ring (which may have an arbitrary substituent). In particular, when KrF laser light is used as the irradiation light, an anthracene ring or an anthracene ring having an arbitrary substituent is used when ArF laser light is used. Preferably, it is a benzene ring or a benzene ring having an arbitrary substituent. Examples of the above-mentioned substituent include a phenolic hydroxyl group, an alcoholic hydroxy φ group, a carboxyl group, a carbonyl group, an ester group, an amine group, or a decylamino group. Examples of the monomer which provides the monomer unit having the above-mentioned absorptive group include stupid ethylene, α-mercaptostyrene, p-methylstyrene, p-butyrylethylene, m-hydroxystyrene, and the like. Ethylenes and their derivatives, substituted or unsubstituted (mercapto) acrylate, substituted or unsubstituted (naphthyl) phthalic acid, substituted or unsubstituted (fluorenyl) yttrium acrylate An aromatic-containing ester having an ethylenic double bond such as an oxime ester. In particular, from the viewpoint of good developability and high resolution, it is preferably an antireflection having a protected or unprotected phenolic hydroxyl group as a light absorbing group. The monomer unit and the monomer having the above-mentioned light absorbing group can be, for example, exemplified by the purpose of 丙烯酸 、 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The monomer unit (00 mol/°) towel is preferably 10 mol% to 100 mol%. The copolymer of λ! is preferably, for example, having a viscosity to flow into the narrow =:= viscosity, and in order to avoid In contrast to the anti-mite resistance, a monomer unit having a reactive functional group which can be cured by reaction with a curing agent or the like is contained. The acid product is exemplified by a phenylene group and a stupid ethylene compound, a (meth) propylene group, and a (meth) group. a copolymer of a monomer such as an ester. An example of a copolymer for a top coat used in a sub-layer is: a monomer having a monomer unit, a monomer, a monomer, and a monomer unit ( ~ monomer unit Α separate heart:: two body comparison: poly /: obtained. The monomer preferably has (meth) two _ vinegar for the wavelength line free radical polymerization. Especially 'high. 曰対 / skin length 25 The transparency of exposure light below 〇nm makes it suitable for [body 2 = polymer] [monomer unit with acid detachment group. monomer] 201222146 WZ66pif anti-clamping agent The copolymer preferably has an acid-releasing group. The term "acid-releasing group" means a group having a bond which is cleaved by an acid, and means a part or all of a group which is desorbed by == citric acid The self-polymerization "polymerization of anti-surname agent" contains a polymer having an acid-decomposable group and a decoloration of the acid component to dissolve the insoluble layer to form a resist pattern.

作為具有酸脫離性基的單體單元，可列舉源自公知的 具有酸脫離性基的單體的單體單元。 具有酸麟縣的單辟元的關_光度及解析度 的觀點“，於構絲合物的財單料元（1⑻莫耳 之中，較佳為20莫耳％以上，更佳為25莫耳％以上。另 外，就對於基板等的密接性的觀點而言，較佳為6〇莫耳％ 以下更佳為55莫耳％以下，進而更佳為％莫耳％以下。 〃有1脫離性基的單體只要是具有酸脫離性基及聚合 I·生夕重鍵的化σ物即可，可使用公知的化合物。所謂聚合 性多重鍵’是指於聚合反麟開裂而形成共聚合鏈的多重 鍵，較佳為乙烯性雙鍵。 作為具有酸脫離性基的單體的具體例，可列舉具有碳 數6〜20❸脂壤式煙&amp;、且具有酸脫離性基的（曱基)丙稀 酸醋。該脂環式煙基可與構成（曱基)丙烯酸醋的醋鍵的氧 原子直接鍵結’亦可經由伸烧基等連結基而鍵結。 該（曱基)丙烯酸酉旨包括：具有碳數6〜2〇的脂環式煙 基’並且該脂環式煙基與構成（曱基)丙稀酸醋的醋鍵的氧 25 201222146 原子的鍵結部位上具有三級碳原子的（曱基）丙烯酸酯；或 者具有碳數6〜20的脂環式烴基，並且_c〇〇R* (R表示 y具有取代基的三級烴基、四氫呋喃基、四氫吡喃基、或 氧雜％庚基）直接或經由連結基而鍵結於該脂環式烴基上 的（曱基）丙稀酸酯。 尤其，當製造適用於藉由波長250 nm以下的光進行 曝光的圖案形成方法的抗姓劑組成物時，作為具有酸脫離 性基的單體的較佳例，例如可列舉：（甲基）丙烯酸2_曱基 -2-金剛烷酯、（曱基）丙烯酸2_乙基_2_金剛烷酯、（曱基)丙 鲁 烯酸2-異丙基_2·金剛烷酯、（甲基）丙烯酸H1，_金剛烷 基M_曱基乙酯、（甲基)丙烯酸丨·甲基環己酯、（曱基)丙烯 酸1-乙基環己醋、（甲基）丙烯酸^曱基環戊醋、（曱基）丙 婦酉文1-乙基環戊酯、（甲基）丙稀酸丨_乙基環辛酯等。 該些之中’更佳為甲基丙烯酸^乙基環己醋（實例的 、曱基丙烯酸2-乙基_2_金剛烷酯（實例的m_5)、甲 基丙烯，2-曱基-2-金剛烷酯（實例的❿⑴、甲基丙稀酸 h乙基環戊醋、（甲基)丙烯酸2_異丙基·2_金剛烧醋。 具有酸脫離性基的單體可單獨使用W，亦可將 · 以上組合使用。 [具有極性基的單體單元.單體] 所謂「極性基」’是指含有具有極性的官能基或具有極 杜的原子團的基’作為具體例，可列舉：羧基、氰基、燒 氧基、缓基、胺基、幾基、含氟原子的基、含硫原子的基、 吞内酯骨架的基、含縮醛結構的基、含醚鍵的基等。 26 201222146 4U288p!f 該些之中，較料_ 進行曝光的圖案形成方法的抗_用皮===光 ;，單體單元作為具有極性基的單=含= =述的具有親水性基的單體單元作為具二=: (具有内酯骨架的單體單元.單體） 匕作為内酉旨骨架，例如可列舉4員環〜 酯骨架。内酯骨架可為僅具有内酽、'&quot;、 環與^族或芳香族的碳環或雜環進亦可使内醋 就對:=的單體單元時，其含量 草耳。/、夕士 的觀點έ ’於所有單體單元（1〇0 t = 佳為 35 莫耳。/。 莫耳0/ 錢光度及解析度的觀點而言，較佳為60 下’更佳為55莫耳％以下，進而更佳為％莫耳％ 骨加ΙϊίΓ㈣骨架的單體單元，可列舉源自具有内酉旨 月％的早體的單體單元。 異二骨架的單體’就對於基板等的密接性優 而δ ’較佳為選自由具有經取代或未經取代的δ-=的（甲基)__、具有經取代或未經取代的丫_ 酉曰％的單體所組成的組群中的至少i種，特佳為具有 未經取代的γ-丁内酯環的單體。 作為具有内酯骨架的單體的具體例， 甲基） 27 201222146 醋、β·(甲基)丙烯醯氧基-γ- 丁内g旨、p_(甲基)丙稀酿氧 T基丁内酯、〇K甲基)丙烯醯氧基_γ_丁内酯、2_(1 ^ 丙烯醯氧基）乙基_4_ 丁内酯、（甲基)丙稀酸泛酸内酯； 丙稀醯氧基-2,6·随紐_、8_甲基丙稀醯氧基·4_ 氧雜二環[5.2.1.02,6]癸烧_3_酮、9_f基丙烯醯氧基_ =⑽們魏·3娜。糾，作為射類似結= 早體，亦可列舉甲基丙烯醯氧基丁二酸酐等。 5亥些之中’更佳為α_甲基丙婦醯氧基个丁内醋（實 、m-U、（X-丙烯醯氧基_γ_ 丁内酯（實例的m-4)、5 丙烯醯氧基-2,6-降莰烷羧内酯、8_甲基醯 ς 三環[5·2.1·〇2勹癸烷_3_酮。 土乳雜 具有内S旨骨架的單體可單獨使们種，亦可將2種 上組合使用。 (具有親水性基的單體單元，單體） 本說明書中的「親水性基」是指（(CM痛、經基、 虱基、甲氧基、羧基及胺基的至少丨種。 該些之中，較佳為適用於藉由波長25〇 μ以下的 氰成方法_劑用共聚合物具有經基或 圖幸物中的具有親水性基的單體單元的含量就抗蝕 击、^的觀點而言’於所有單體單元（刚莫耳 。/以^較佳為5莫耳％〜40莫耳％。上限值更佳為35莫耳 二更佳為3。莫耳❶，°以下，特佳為25莫耳％以下。 下限值更佳為10莫耳％以上。 28 201222146 ^υζόόριί 作為具有親水性基的單體，例如可 ί的7 Μ酯；單體的親賴基上歸烧基、Ϊ i)丙二的街生物’具有環式煙基的單體（例如（ΐ 土）烯-文衣己酯、（甲基)丙烯酸丨·異莰酯、（甲基)丙 金岡^旨、(甲基)丙稀酸三環癸酿、( -夂 (甲基)丙稀酸2_甲基I金剛_、（甲基)丙婦酸2•乙ΐ；、 金剛烧m⑽、乙烯基萘、（曱基)丙烯酸萘§旨、（甲The monomer unit having an acid-releasing group may, for example, be a monomer unit derived from a known monomer having an acid-releasing group. It has the viewpoint of the luminosity and resolution of the single-prime yuan of the acid lining county, and the financial element of the constitutive filament compound (1 (8) molar, preferably 20 mol% or more, more preferably 25 mo In view of the adhesion between the substrate and the like, it is preferably 6 〇 mol% or less, more preferably 55 mol% or less, and still more preferably % mol% or less. The monomer of the group may be a ruthenium compound having an acid detachment group and a polymerization I 生 重 bond, and a known compound may be used. The term "polymerizable multiple bond" means that the polymerization is formed by polymerization and reverse cleavage. The multiple bond of the chain is preferably an ethylenic double bond. Specific examples of the monomer having an acid-releasing group include a carbon 6 to 20 ❸ 壤 式 &&amp; Acrylic vinegar. The alicyclic nicotinyl group may be directly bonded to an oxygen atom constituting the vinegar bond of (mercapto)acrylic acid vinegar, and may also be bonded via a linking group such as a stretching group. Acrylic acid is intended to include: an alicyclic nicotinyl group having a carbon number of 6 to 2 Å and the alicyclic nicotine group and the constituent (mercapto) propyl group The vinegar-bonded oxygen of the dilute vinegar 25 201222146 (indenyl) acrylate having a tertiary carbon atom at the bonding site of the atom; or an alicyclic hydrocarbon group having a carbon number of 6 to 20, and _c〇〇R* ( R represents a ternary hydrocarbon group having a substituent of y, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxahyl heptyl group, which is bonded to the alicyclic hydrocarbon group directly or via a linking group. In particular, when producing an anti-surname composition suitable for a pattern forming method of exposure by light having a wavelength of 250 nm or less, as a preferred example of the monomer having an acid-releasing group, for example, 2) fluorenyl-2-adamantyl acrylate, 2 -ethyl 2 -adamantyl (meth) acrylate, 2-isopropyl 2 - adamantyl (mercapto) acrylate (meth)acrylic acid H1,_adamantyl M_mercaptoethyl ester, bismuth methyl hexyl methacrylate, 1-ethylcyclohexyl acrylate (meth) acrylate, (meth) acrylate ^ Mercaptocyclopentyl vinegar, (mercapto), propyl ethyl ketone, 1-ethylcyclopentyl ester, (methyl) bismuth acrylate, ethyl cyclooctyl ester, etc. Among these, 'better Ethylcyclohexyl acrylate (example, 2-ethyl 2 -adamantyl methacrylate (example m_5), methacryl, 2-mercapto-2-adamantyl ester (example ❿(1), Methyl acrylic acid, hethylcyclopentaacetic acid, (meth)acrylic acid, 2-isopropylidene 2, ruthenium vinegar. The monomer having an acid detachment group may be used singly or in combination of the above. [Monomer unit having a polar group. Monomer] The term "polar group" means a group containing a functional group having a polar group or an atomic group having a polar group. Specific examples thereof include a carboxyl group, a cyano group, and an alkoxy group. , a molybdenum group, an amine group, a aryl group, a fluorine atom-containing group, a sulfur atom-containing group, a swallow lactone skeleton group, an acetal structure-containing group, an ether bond-containing group, etc. 26 201222146 4U288p!f Among them, the anti-skin === light of the pattern forming method for performing exposure; the monomer unit as a single unit having a polar group = the monomer unit having a hydrophilic group as described == (Monomer unit having a lactone skeleton. Monomer) The oxime is an internal skeleton, and examples thereof include a 4-membered ring-ester skeleton. The lactone skeleton may be a carbocyclic or heterocyclic ring having only internal oxime, '&quot;, ring and group or aromatic, or the internal vinegar may be the same as the monomer unit of ==. /, Xi Shi's point of view έ 'In all monomer units (1〇0 t = good for 35 moles. /. Moer 0 / money luminosity and resolution point of view, preferably 60 times 'better 55% by mole or less, more preferably %% by mole. The monomer unit of the skeleton (4) skeleton may be a monomer unit derived from an early body having a % of the internal phase. The adhesion of the substrate or the like is excellent, and δ ' is preferably selected from the group consisting of a monomer having a substituted or unsubstituted δ-= (meth)__, having a substituted or unsubstituted 丫_酉曰%. At least i of the group, particularly preferably a monomer having an unsubstituted γ-butyrolactone ring. As a specific example of a monomer having a lactone skeleton, methyl) 27 201222146 vinegar, β·(A醯 醯 醯 醯 - γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ醯oxy)ethyl_4_butyrolactone, (meth)acrylic acid pantolactone; acetamidooxy-2,6·hexanyl, 8-methylpropenyloxy-4_oxa Second ring [5.2.1.02,6] 癸3_ ketone, 9_f propyl Acyl group _ = ⑽ are Wei-Na 3. Correction, as a shot similar to the early body, may also be exemplified by methacryloxy succinic anhydride. Among the 5 hai, 'better is α_methyl propyl sulfonate butyl vinegar (real, mU, (X-propylene methoxy _ γ - butyrolactone (example m-4), 5 propylene oxime Oxy-2,6-norbornane carboxy lactone, 8-methyl hydrazine tricyclo[5·2.1·〇2 decane _3 ketone. The monomer of the organic latex having the internal S chain can be used alone. It can also be used in combination of two kinds. (Polymer unit having a hydrophilic group, monomer) The "hydrophilic group" in the present specification means ((CM pain, warp group, thiol group, methoxy group) At least one of a group, a carboxyl group and an amine group. Among them, a cyanine forming method suitable for a wavelength of 25 μm or less is preferred. The copolymer for the agent has a hydrophilicity in a radical or a graph. The content of the monomer unit of the group is in terms of resisting, and is in all monomer units (just Mohr. / is preferably 5 mol% to 40 mol%. The upper limit is more preferably 35 Mo Er 2 is preferably 3. Mo Mo, below, particularly preferably 25 mol% or less. The lower limit is more preferably 10 mol% or more. 28 201222146 ^υζόόριί as a monomer having a hydrophilic group, For example, 7 oxime esters; monomeric赖基上上烧基,Ϊ i) 丙二的街生物' monomers with ring-type nicotine (such as (alkali) ene-hexyl hexyl ester, bismuth (meth) acrylate) Base), (methyl) acrylic acid tricyclic brewing, ( - 夂 (methyl) acrylic acid 2 - methyl I jing _, (methyl) propyl benzoic acid 2 ΐ ΐ; Emery m (10), vinyl naphthalene, (indenyl) acrylate naphthene

丙烯酸fs旨、（甲基)丙烯酸苯§旨等）含有雜、羧基等^ 水性基作為取代基的單體。 〃 作為具有親水性基的單體的具體例，可列舉：（甲基 丙烯酸（實例的m-10)、（曱基)丙烯酸2減乙醋（實^ 的m-7)、（甲基）丙烯酸3_羥基丙酯、（甲基)丙烯酸2-羥基_ 正丙醋、（曱基)丙稀酸4_經基丁g旨、（曱基)丙烯酸3_經基 金剛烷酯、（曱基)丙烯酸2_或3_氰基_5_降莰酯、（甲基)丙 烯酸2·氰基甲基-2-金剛烷酯等、羥基苯乙烯、羥基乙烯基 萘。就對於基板等的密接性的觀點而言，較佳為（曱基）丙 烯酸3·羥基金剛烷酯、（曱基)丙烯酸2_或3_氰基_5_降莰 酯、（曱基)丙烯酸2-氰基曱基_2-金剛烷酯等。 該些之中’更佳為曱基丙烯酸3_羥基金剛烷酯（實例 的m-3)、曱基丙烯酸2_氰基曱基-2-金剛烷酯、羥基苯乙 烯、羥基乙烯基萘（實例的m_12)。 具有親水性基的單體可單獨使用1種，亦可將2種以 上組合使用。 [其他單體單元·單體] 29 201222146κ 聚合物（ρ)相 (其他單體）衍需要可含有自上述以外的公知的單體 :50 nm以下的止出的單體單元。例如’適用於藉由波長 以下的来、/ 174&quot; 聚合物可含有自進仃曝光的圖案形成方法的抗蝕劑用共 的單體衍生㈣單^化學式⑴或化學式㈤所表示 [&gt;ib 1] 早兀*°A monomer containing a water-based group such as a hetero or a carboxyl group as a substituent, such as acrylic acid fs or (meth)acrylic acid. 〃 Specific examples of the monomer having a hydrophilic group include (methacrylic acid (example m-10), (mercapto)acrylic acid 2 minus vinegar (m-7 of real ^), (methyl) 3-hydroxypropyl acrylate, 2-hydroxy-n-propyl acrylate (meth) acrylate, (mercapto) acrylic acid 4 _ butyl ketone, (mercapto) acrylic acid 3_ via fundane ester, (曱Base) acrylic acid 2_ or 3_cyano_5_norbornyl ester, (meth)acrylic acid 2 · cyanomethyl-2-adamantyl ester, etc., hydroxystyrene, hydroxyvinyl naphthalene. From the viewpoint of adhesion, 3 (hydroxy)adamantyl (meth) acrylate, 2 or 3 - cyano 5 - norbornyl (meth) acrylate, 2-cyano (meth) acrylate Mercapto- 2 -adamantyl ester, etc. Among them, 'preferably 3 -hydroxyadamantyl methacrylate (example m-3), 2 -cyanononyl-2-adamantyl thioglycolate Hydroxy styrene, hydroxyvinyl naphthalene (example m_12). The monomer having a hydrophilic group may be used singly or in combination of two or more kinds. [Other monomer units/monomers] 29 201222146κ polymer (ρ) phase (other orders It is desirable to include a known monomer other than the above: a monomer unit of 50 nm or less. For example, 'applicable to the wavelength below, / 174&quot; The polymer may contain a pattern of self-exposure exposure. The resist of the formation method is represented by a common monomer (4) represented by the chemical formula (1) or the chemical formula (5) [&gt;ib 1] early 兀*°

...⑴ [化2]...(1) [Chemical 2]

或三氟f基。4〇〜2^(ΉΜ、Η 基、或芳基、钱基或芳基絲、烯基或氧代 放射線或熱喊應而產生 l °ρ為對光化射線 的基。ζ為具有可含有雜原 201222146 4UZ8»pif 的石厌數2〜20的環狀結構的二價的烴基。 作為基P，具體可列舉銃鹽、鏘鹽骨架。 ^合有自以上述化學式（i)或化學式（ii)所表示的單 體柯生出的單體單元的聚合物於聚合物鏈中鍵結有藉由光 化射線或放射線的照射而產生酸的基（化學式⑴或化學 式（U)中的基P)，因此當將含有該聚合物的組成物用於 抗韻劑用途時，酸產生部位均勻地分散，可獲得感光度、 _ 解析性、、圖案粗糖度等優異等的效果，故較佳。 作為其他單體’可辟具有直鏈或分支結構的（甲基) 丙烯酸酯、芳香族烯基化合物、羧酸酐。 乍為/、有直鍵或刀支結構的（甲基）丙稀酸酯的例子， 可列舉·（甲基)丙烯酸甲酿（實例的m_8)、（甲基)丙稀酸 乙酉曰（曱基)丙稀酸2-乙基己酯、（甲基)丙烯酸正丙酯、（甲 f丙稀酸異丙醋、（曱基)丙稀酸丁醋、（曱基)丙婦酸異丁 酉曰、（甲基）丙烯酸甲氧基甲醋、（甲基）丙烯酸正丙氧基乙 % 〗、（甲基)丙烯酸異丙氧基乙醋、（甲基)丙烯酸正丁氧基乙 醋、（曱基)丙烯酸異丁氧基乙醋、（曱基)丙烯酸第三丁氧基 乙醋、（甲基)丙稀酸2-乙氧基乙醋、（甲基)丙烯酸^乙氧 基乙醋、（甲基）丙_ 2,2,2-三氟乙醋、（曱基）丙稀酸 2,2士3_四氟正丙醋、（曱基)丙稀酸2,2,3,3,3-五氣正丙醋、 °K三)氟甲基丙烯酸甲醋、α•(三）氟曱基丙稀酸乙醋、α_㈢ 既甲基丙稀酸2-乙基己g旨、α㈢氟甲基丙稀酸正丙醋、 三)氟甲基丙烯酸異丙酉旨、α_㈢氟曱基丙稀酸正丁基、 心(三)氟甲基丙烯酸異丁酯、α_(三)氟甲基丙烯酸第三丁 31 201222146 醋、α-㈢氣曱基丙稀酸曱氧基曱酿、^(三） ίίΐΓ、α-(三)氟甲基丙烯酸正两氧基乙酿、：(三)氟 ㈢氟甲基丙烯酸異丁氧基乙 烯酸第三丁氧基乙酯等。 、一池肀土内 作為芳香族稀基化合物的例子， 例的m，9)、a•甲基苯乙烯、乙稀基甲苯等。·本乙婦（貝 酐等作為紐針的例子，可列舉：順丁烯二酸野、衣康酸 另外’作為其他單體，乙烯、丙稀 稀、丙歸酿胺、N_甲基丙烯酿胺、N :細咕四 氣乙烯、氟乙嬌、傯-_ 7 ^ ，Ν_—曱基丙烯醯胺、 行共聚合。 一烯、乙烯基吡咯啶_等亦可進 &lt;聚合起始劑&gt; 基者聚為藉t熱而分解並有效率地產生自由 ⑽造用共聚合物時的二 期溫度為耽為使们0小時半衰 的差為urU 1〇小時半衰期溫度與聚合溫度 二▼基的例子’可列舉：2,2，_偶氮雙異丁猜、 猜)似,氮雙=二酸醋、2,2l偶氮雙(2,4_二甲基戍 又 米唑啉_2·基）丙烷J等偶氮化合物，2,5- 32 201222146 ^UZOQpxf ^甲過氧化第三丁基邮、過氧化二碳酸二(4_ 弟二二基壤己基)自旨等有機過氧化物。更佳為·化合物。 ^可自市售品而獲得。例如可較佳地使用二甲基 -口，-偶氮雙異丁酸_ (和光純藥工業公司製造，V·(商 品名）’ 10小時半衰期溫度為66。〇、2,2，-偶氮雙(2,4_二甲 基戊，）（和光純藥工業公司製造，V65 (商品名），10小 時半衰期溫度為5Tc )等。 &lt;溶劑&gt; t合步驟中亦可使用聚合溶劑。作為聚合溶劑，例如 可列舉下述的聚合溶劑。 醚類：鏈狀醚（例如二乙醚、丙二醇單甲基醚（以下， 有時亦 5己作「PGME ( Propylene Glycol Monomethyl Ether)」）等）、環狀醚（例如四氫呋喃（以下，有時亦記 作「THF (Tetrahydrofuran)」）、1，4·二0惡烧等）等。 酯類：乙酸曱酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、 乳酸丁酯、丙二醇單曱醚乙酸酯（以下，有時亦記作 「PGMEA ( Propylene Glycol Monomethyl Ether Acetate)」）、γ·丁内酯等。 酮類：丙酮、曱基乙基酮（以下，有時亦記作「ΜΕΚ (Methyl Ethyl Ketone)」）、曱基異丁基酮（以下，有時亦 吕己作「MIBK (Methyl Isobutyl Ketone)」）、環己_等。 醯胺類：N，N-二曱基乙醯胺、Ν,Ν-二曱基甲醯胺等。 亞颯類：二曱基亞颯等。 芳香族烴：苯、曱苯、二曱苯等。 33 201222146 脂肪族烴··己烷等。 脂環式烴：環己烷等。 聚合溶劑可單獨使用1種，亦可併用2種以上。 ，合溶_使用量並無特麻定，例如較佳為聚合反 ^束時的反應器⑽溶液（聚合反應溶液）的固 濃度成為20質量〇/0〜4〇質量〇/0左右的量。 丑刀 &lt;聚合方法&gt; 作為製造聚合物（Ρ)的聚合方法Or a trifluorof group. 4〇~2^(ΉΜ,Η, or aryl, benzyl or aryl silk, alkenyl or oxo radiation or heat stimuli to produce l °ρ as the basis for actinic rays. Miscellaneous 201222146 4UZ8»pif The divalent hydrocarbon group of the ring structure of 2 to 20 in the stone anisotropy. Specific examples of the base P include a sulfonium salt and a sulfonium salt skeleton. The combination of the above chemical formula (i) or chemical formula ( Ii) The polymer of the monomer unit derived from the monomer is bonded to the polymer chain by a group which generates an acid by irradiation with actinic rays or radiation (the base of the chemical formula (1) or the chemical formula (U) Therefore, when the composition containing the polymer is used for the anti-speech application, the acid-generating portion is uniformly dispersed, and an effect such as sensitivity, _ resolution, and pattern coarseness can be obtained, which is preferable. As another monomer, a (meth) acrylate having a linear or branched structure, an aromatic alkenyl compound, a carboxylic acid anhydride, or a (meth) acrylate having a linear bond or a knive structure For example, (meth)acrylic brewing (example m_8), (meth)acrylic acid酉曰(曱基)2-ethylhexyl acrylate, n-propyl (meth) acrylate, (isopropyl isopropyl acrylate, butyl acetonate, butyl acrylate) Isobutyral acid, methoxymethyl (meth)acrylate, n-propoxyethyl (meth)acrylate, isopropoxyacetic acid (meth)acrylate, n-butoxy (meth)acrylate Ethyl vinegar, (meth)acrylic acid isobutoxyacetic acid, (mercapto)acrylic acid tert-butoxyacetic acid, (meth)acrylic acid 2-ethoxyethyl acetonate, (meth)acrylic acid^ Ethoxyethyl vinegar, (meth) propyl 2,2,2-trifluoroethyl vinegar, (mercapto) acrylic acid 2,2 士 3 _ tetrafluoro propylene vinegar, (mercapto) acrylic acid 2 , 2,3,3,3-penta-n-propyl vinegar, °K3) fluoromethyl methacrylate, α•(III) fluoroanthryl acrylate, α_(III) methacrylic acid 2-B Glycerin, α(tri)fluoromethylpropionic acid n-propyl vinegar, c) isopropyl fluoromethacrylate, α-(tri)fluoroanthryl propyl acrylate, isobutyl fluoromethacrylate, __(tri)fluoromethacrylic acid third butyl 31 201222146 vinegar, α-(three) gas thiol acrylate acid 曱, ^ (3) ί ΐΓ, α-(tri)fluoromethacrylic acid, n-oxyethylene, (3) fluoro (tri) fluoromethacrylic acid, isobutoxyacetic acid, tert-butoxyethyl ester, and the like. In the pool of alumina, as an example of the aromatic dilute compound, m, 9), a. methyl styrene, ethylene toluene, and the like. ·This woman (bean anhydride, etc. as an example of a needle, may be exemplified by: maleic acid, itaconic acid as another monomer, ethylene, propylene, propylene, N-methyl propylene Amine, N: fine tetrakiethylene, fluoroethylene, 偬-_ 7 ^, Ν_-mercapto acrylamide, copolymerization. Monoolefin, vinyl pyrrolidine _, etc. can also enter the polymerization start Agent> The base is decomposed by the heat of t and efficiently produced. (10) The second-stage temperature when the copolymer is used is 耽 so that the difference of 0-hour half-life is urU 1 〇 half-life temperature and polymerization temperature. The example of the two ▼ base can be enumerated: 2, 2, _ azobisisodin, guess, nitrogen double = diacid vinegar, 2, 2l azobis (2,4 dimethyl hydrazine and carbazole Azo compound such as porphyrin-2·yl)propane J, 2,5- 32 201222146 ^UZOQpxf ^T-butyl peroxymethyl peroxide, diperoxydicarbonate di(4_dioxacarbyl) Oxide. More preferably, a compound. ^ Available from commercial products. For example, dimethyl-port,-azobisisobutyric acid (manufactured by Wako Pure Chemical Industries, Ltd., V. (trade name)' 10 hour half-life temperature of 66. 〇, 2, 2, - even can be preferably used. Nitrogen bis(2,4-dimethyl pentane) (manufactured by Wako Pure Chemical Industries, Ltd., V65 (trade name), 10-hour half-life temperature: 5Tc), etc. &lt;Solvent&gt; Examples of the polymerization solvent include the following polymerization solvents: ethers: chain ethers (for example, diethyl ether or propylene glycol monomethyl ether (hereinafter, sometimes referred to as "PGME (Proylene Glycol Monomethyl Ether)") ), a cyclic ether (for example, tetrahydrofuran (hereinafter sometimes referred to as "THF (Tetrahydrofuran)"), 1,4-(0), etc.). Ester: decyl acetate, ethyl acetate, butyl acetate Ethyl lactate, butyl lactate, propylene glycol monoterpene ether acetate (hereinafter sometimes referred to as "PGMEA (Proylene Glycol Monomethyl Ether Acetate)"), γ·butyrolactone, etc. Ketones: acetone, sulfhydryl Ethyl ketone (hereinafter sometimes referred to as "Methyl Ethyl Ketone"), Isobutyl ketone (hereinafter, sometimes referred to as "MIBK (Methyl Isobutyl Ketone)"), cyclohexanyl, etc. Hydramides: N,N-dimercaptoacetamide, hydrazine, hydrazine-dioxin Mercaptoamine, etc. Athene: Dimercaptopurine, etc. Aromatic hydrocarbons: benzene, toluene, diphenyl, etc. 33 201222146 Aliphatic hydrocarbons··hexane, etc. Alicyclic hydrocarbon: cyclohexane The polymerization solvent may be used singly or in combination of two or more. The amount of the solvent to be used is not particularly limited, and for example, it is preferably a solution of the reactor (10) solution (polymerization solution) at the time of polymerization reaction. The concentration is an amount of about 20 mass 〇 /0 to 4 〇 mass 〇 /0. Ugly knife &lt;polymerization method&gt; As a polymerization method for producing a polymer (Ρ)

懸濁聚合法、乳化聚合二公= 二=^^使光線透過ί 點，及可使共聚合物的分子_丄=早體的步驟的觀 佳為溶液聚合法。 較低的觀點而言，較 溶液聚合法例如可為將Suspension polymerization, emulsion polymerization, two = two = ^ ^ light transmission through the ί point, and the molecular _ 丄 = early step of the copolymer is better than the solution polymerization method. From a lower point of view, the solution polymerization method can be, for example,

内進行反應的方法（以下，曰斤有早體加入至反應器 同-^類的單體單元❾：„ 3批、量方^)’但就易於製造 而言’較佳為藉由滴力二的共聚合物的觀點 劑的滴加聚合法。滴加聚^ ^給早體及聚合起始 聚合物的所有單體供終」句稽由滴加來將用於合成 下，有時亦稱為整體滴至反應器内的溶劑中的方法（以 分加入至反應器内，缺:方式）’亦可為事先將單體的一部 時亦稱為部分滴加方^滴加剩餘單體的方法（以下，有 特佳為以下的眾合方 合方法（Z1)是以於 〆或聚合方法（Z2)。聚 °反應的初期，使所生成的共聚合 34 201222146 ΗΌΖόόρϊί 物的早體=成的偏差變小的方式進行控制的方法，聚合方 法（Z2)是以於聚合反應的初期及後期，使所生成的共聚 合物的單體組成的偏差變小的方式進行控制的方法。 &lt;聚合方法（Z1) &gt; 事先向反應益内加入以第〗組成含有單體的第i溶 液’將反應器内加熱至規定的聚合溫度為止後，向反應器 内滴加含有單體的1種以上的滴加溶液。再者，第丨溶液 φ 亦可藉由滴加等而緩慢地供給至反應器内。 假疋不事先向反應器内加入單體，而以固定時間均勻 地滴加單體組成與滴加溶液相同的溶液，則共聚合反應中 的單體消耗速度快的單體於聚合初期被以少於所期望的組 成比的比例添加至共聚合物中，而引起單體組成及鏈結構 的偏差。 因此，本方法中，較佳為於事先加入至反應器内的第 1溶液中，使單體消耗速度慢的單體的組成比（含有比率） 大於聚合反應中所使用的所有溶液的總量中的該單體的組 響 成比。 具體而言，較佳為如下的聚合方法：一邊向反應器内 滴加單體及聚合起始劑，一邊於上述反應器内使2種以上 的單體q〜單體αη (η為2以上的整數）進行聚合，而獲 得包含構成單元吣〜構成單元α，η (其中，吣〜α，η表示分 別自單體αι〜單體αη衍生出的單體單元）的聚合物， 且具有下述（VI)及下述（VII)的步驟。 (VI)於向反應器内滴加聚合起始劑之前、或與開始 35 201222146 I土〆 Ai 滴加^起始劑的同時，向上述反應器内供給第^溶液的 v驟4第1溶液是以對應於各單體的反應性比，自聚合 勒期於穩定狀態下使各單體進行聚合的比例的第i組成含 有單體％〜單體％的溶液； (I11?當表示欲獲得的聚合物（Ρ)中的構成單元α，ι ，構成單tl 〇^的含有比率的目標組成（單位：莫耳％)為 Τ _ 012 ♦ ··. · α'η時，於向上述反應器内開始供給上述第1 溶液之後、或與開始供給上述第i溶液的同時，供給以與 上述目標組成相同的組成含有上述單體％〜單體％的第2 φ 溶液的步驟。 、·=该方法中，上述第1組成是以如下方式設計的組 成·右於反應器内所存在的單體的含有比率為第！组成時 向該反應器内滴加上述第2溶液，則剛滴加之後所生成的 聚合物分子的構成單元的含有比率成為與目標組成相同。 於此情況下，由於剛滴加之後所生成的聚合物分子中 的構成單元的含有比率與所滴加的第2溶液中的單體的含 有比率（目標組成）相同’因此剛滴加之後殘存於反應$ 内的單體的含有比率始終成為固定（第】組成）。因此若 · 向該反應器内継續滴加第2溶液’則可獲得始終持續生成 目標組成的聚合物分子的穩定狀態。 &lt;聚合方法（Z2) &gt; ^進而，共聚合反應中的單體消耗速度慢的單體於聚合 後期被以多於所期望的組成比的比例添加至共聚合物中， 而引起單體組成及鏈結構的偏差。 36 201222146 HUZOdpif 因此，本方法中，就更容易製造 少的共^合物的觀點而言，較佳為於將 ==止後’準備2種以上供給至反應器内= 液，並於聚合初期與聚合後期改變滴加溶 情況下，在第2溶液的滴加結束後= 成/、°玄二/奋液不同的滴加溶液（第3溶液）。The method of carrying out the reaction (hereinafter, the monomer is added to the reactor and the monomer unit of the same type: „3 batches, measuring amount ^)” but it is preferably made by the force of being easy to manufacture. A method of dropwise addition polymerization of a co-polymeric viewpoint of a second polymer. The addition of all the monomers of the early polymer and the starting polymer of the polymerization is added to the final sample. The addition is used for the synthesis, and sometimes The method of dropping the whole into the solvent in the reactor (adding to the reactor in the absence of the method) can also be used to add a part of the monomer to the part of the monomer in advance. The method of the body (hereinafter, it is particularly preferred that the following method (Z1) is based on the hydrazine or the polymerization method (Z2). In the initial stage of the polymerization, the resulting copolymerization 34 201222146 ΗΌΖόόρϊί The method of controlling the method in which the variation is small, and the polymerization method (Z2) is a method of controlling the variation in the monomer composition of the produced copolymer in the initial stage and the later stage of the polymerization reaction. &lt;Polymerization method (Z1) &gt; Adding to the reaction benefit in advance After the inside of the reactor is heated to a predetermined polymerization temperature, one or more dropping solutions containing a monomer are added dropwise to the reactor. Further, the second solution φ can also be added dropwise. Waiting slowly and slowly into the reactor. If the monomer is not added to the reactor in advance, and the same solution of the monomer composition and the dropping solution is uniformly added at a fixed time, the monomer consumption in the copolymerization reaction is carried out. The fast-moving monomer is added to the copolymer at a ratio less than the desired composition ratio at the initial stage of polymerization, causing variations in monomer composition and chain structure. Therefore, in the present method, it is preferred to add to the prior In the first solution in the reactor, the composition ratio (content ratio) of the monomer having a slow rate of monomer consumption is larger than the composition ratio of the monomer in the total amount of all the solutions used in the polymerization reaction. In the polymerization method, two or more kinds of monomers q to monomers αη (η is an integer of 2 or more) in the reactor while dropping a monomer and a polymerization initiator into the reactor. ) to perform the aggregation and get the inclusion a unit cell 吣 constituting a unit α, η (where 吣 α α, η represents a monomer unit derived from a monomer α 〜 monomer α η, respectively), and has the following (VI) and the following (VII) (VI) before the dropwise addition of the polymerization initiator to the reactor, or to the start of the addition of the starting agent at the beginning of 35 201222146 I soil Ai, the v solution of the first solution is supplied to the reactor. 4: The first solution is a solution containing a monomer % to a monomer % in a ratio of a ratio corresponding to a reactivity ratio of each monomer to a ratio of polymerization of each monomer in a stable state from a polymerization period; (I11? When the constituent unit α, ι in the polymer (Ρ) to be obtained is expressed, the target composition (unit: mole %) constituting the content ratio of tl 〇 ^ is Τ _ 012 ♦ ··· · α'η, The step of supplying the second φ solution containing the monomer % to monomer % in the same composition as the target composition after the supply of the first solution to the reactor or the supply of the ith solution is started. . In the method, the first composition is designed as follows: The content ratio of the monomer present in the reactor is the same as that of the first composition! In the composition, the second solution is added dropwise to the reactor, and the content ratio of the constituent units of the polymer molecules formed immediately after the dropwise addition is the same as the target composition. In this case, since the content ratio of the constituent unit in the polymer molecule formed immediately after the dropwise addition is the same as the content ratio (target composition) of the monomer in the second solution to be dropped, it remains after the addition. The content ratio of the monomer in the reaction amount is always fixed (the first component). Therefore, if the second solution is continuously dropped into the reactor, a stable state in which the polymer molecules of the target composition are continuously formed can be obtained. &lt;Polymerization Method (Z2) &gt; ^ Further, the monomer having a slow rate of monomer consumption in the copolymerization reaction is added to the copolymer at a ratio of more than the desired composition ratio at the later stage of polymerization, causing a monomer Composition and chain structure deviation. 36 201222146 HUZOdpif Therefore, in the present method, in view of the fact that it is easier to produce a small amount of a common compound, it is preferable to supply two or more kinds of preparations to the inside of the reactor = after the == stop, and in the initial stage of polymerization. In the case where the dropwise addition is dissolved in the late stage of polymerization, after the completion of the dropwise addition of the second solution, a dropping solution (third solution) having a different ratio of /, ° Xuan Er / Fen liquid is obtained.

2合仙滴加的滴加溶_佳為賴雜速度最慢 於目標組成，更佳為不含單難耗速度i 較佳為於聚合後期滴加的滴加溶液中： 合叶量為總單體供給量的αι質量％〜10質 Γ:量Γ為1質量%〜7·5質量… 可包聚合方法(Ζ2” ’聚合起始劑 至反應如。㈣加溶液巾’亦可與單體分開來滴加 、祕直至滴加結束為止為固定，亦可結合單體 行。夕6又土變化。滴加可連續地進行，亦可間歇地進 聚合溫度較佳為50¾〜15〇艺。 &lt;精製方法&gt; 視需要，利用1 4 叩二噁烷、丙酮、THF、MKC、MIBK、 37 201222146 1 W KJ W J-mf Λ-Λ. γ- 丁内醋、PGMEA、PGME、二甲基曱醯胺 (Dimethylforaiamide ’ DMF)等良溶劑將藉由溶液聚合所 製造的共聚合物溶液稀釋成適當的溶液黏度後，將其滴加 至甲醇、水、己烷、庚烷等大量的不良溶劑中而使共聚合 物析出。該步驟通常被稱為再沈澱，對於去除聚合溶液中 所殘存的未反應的單體或聚合起始劑等非常有效。 該些未反應物若維持原樣而殘存，則有可能對抗餘劑 性能造成不良影響，因此較佳為儘可能將其去除。再沈澱 步驟有時亦不需要。其後，將其析出物濾除，充分地乾燥 鲁 而獲得共聚合物。另外，亦可於濾除析出物後，不進行乾 燥而以濕粉的狀態使用。 另外，所製造的共聚合物溶液亦可直接用作抗蝕劑組 成物、或者利用適當的溶劑稀釋後用作抗蝕劑組成物。此 時，可適宜添加保存穩定劑等添加劑。 &lt;微景；^製程用共聚合物的製造方法的實施形態（Z2,） &gt; 作為使用以於聚合反應的初期及後期’所生成的共聚 · 合物的單體組成的偏差變小的方式進行控制的方法（聚合 方法（Z2))製造微影製程用共聚合物的方法，較佳為以 下的方法（微影製程用共聚合物的製造方法的實施形態 (Z2，））。 本實施形態的製造方法包括一邊向反應器内滴加單體 及聚合起始劑’ 一邊於該反應器内使2種以上的單體％〜 單體αη進行聚合’而獲得包含單體單元a〜單體單元α，η 38 201222146 H-UZOOpif 的聚合物（P)的聚合步驟。 該聚合步驟是利用自由基聚合法來進行，本實施形態 中，利用一邊向反應器内滴加單體及聚合起始劑，一邊於 該反應器内進行聚合的滴加聚合法。2 仙 滴 滴 Add 滴 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The amount of monomer supply is from 1% by mass to 10% by mass: the amount is 11% by mass to 7.5% by mass. The polymerization method can be used (Ζ2" 'polymerization initiator to reaction. (4) solution towel can also be used with The body is separated and added, and the secret is fixed until the end of the addition, and the monomer row can also be combined. The eve 6 and the soil change. The dropwise addition can be carried out continuously, or the polymerization temperature can be intermittently preferably 503⁄4~15. &lt;Refining method&gt; 1 4 叩dioxane, acetone, THF, MKC, MIBK, 37 201222146 1 W KJ W J-mf Λ-Λ. γ-butane vinegar, PGMEA, PGME, two A good solvent such as Dimethylforaiamide 'DMF is diluted with a copolymer solution prepared by solution polymerization to a suitable solution viscosity, and then added dropwise to a large amount of methanol, water, hexane, heptane, and the like. The co-polymer is precipitated in a poor solvent. This step is often referred to as reprecipitation and is removed for removal of the polymerization solution. Unreacted monomers, polymerization initiators, etc. are very effective. If the unreacted materials remain as they are, there is a possibility of adversely affecting the performance of the residual agent, so it is preferred to remove them as much as possible. After that, the precipitates are filtered out, and the precipitates are sufficiently dried to obtain a copolymer. Alternatively, the precipitates may be filtered off and dried in a wet powder state without being dried. The produced copolymer solution may be used as a resist composition as it is, or may be used as a resist composition after being diluted with a suitable solvent. In this case, an additive such as a storage stabilizer may be appropriately added. (Embodiment of the method for producing a copolymer for a process) (Z2) &gt; A method of controlling the variation in the monomer composition of the copolymer compound formed in the initial stage and the latter stage of the polymerization reaction is small ( Polymerization method (Z2)) A method for producing a copolymer for a lithography process is preferably the following method (embodiment (Z2) of a method for producing a eutectic copolymer). The method comprises the steps of: adding a monomer and a polymerization initiator to the reactor while polymerizing two or more monomer % to monomer αη in the reactor to obtain a monomer unit a to a monomer unit. α,η 38 201222146 H-UZOOpif polymer (P) polymerization step. The polymerization step is carried out by a radical polymerization method. In the present embodiment, a monomer and a polymerization initiator are added dropwise to the reactor. A dropping polymerization method in which polymerization is carried out in the reactor.

本實施形態中，使用含有單體的溶液Sa (3為i〜d， d為1以上的整數）、溶液Tb㈧為丨〜e，6為丨以上的整 數）、溶液Uc(c為1〜f，f4l以上的整數）。溶液Sa、 溶液Tb、溶液〜Uc較佳為含有溶劑。 本實施形態中的聚合步驟包括：分別向反應 器内供給 溶液Sa、溶液Tb的主步驟、及於該溶液％及溶液几的 供給結束後將溶液Uc供給至反應器内的後步驟。 &lt;主步驟&gt; 首先，對主步驟進行說明。 [溶液Tb] 浴狀π疋王步驟中所使用的溶液T1、^ 為1以上的整數）的總稱。作為溶液Tb，可僅使用i種溶 液（僅使用τυ，亦可使用2種以上的溶液（T1、T2...Te)。 e的上限值並無特別限定’但若較多，則操作會變得繁靖， 因此貫質上較佳為4以下，更佳為3以下。 溶液Tb巾的賴的含有比率（第 獲得的聚合物（P)中的單體單元. 比率的目標組成相同。 2組成）與表示欲 早體早元α'η的含有 Τ1 39In the present embodiment, a solution Sa containing a monomer (3 is i to d, d is an integer of 1 or more), a solution Tb (eight) is 丨~e, 6 is an integer of 丨 or more, and a solution Uc (c is 1 to f) is used. , an integer above f4l). The solution Sa, the solution Tb, and the solution ~Uc preferably contain a solvent. The polymerization step in the present embodiment includes a main step of supplying the solution Sa and the solution Tb into the reactor, and a subsequent step of supplying the solution Uc to the reactor after the supply of the solution % and the solution is completed. &lt;Main Step&gt; First, the main step will be described. [Solution Tb] A general term for the solutions T1 and ^ used in the bath-like π- 疋 step are integers of 1 or more. As the solution Tb, only one type of solution may be used (only τυ may be used, or two or more kinds of solutions (T1, T2, ... Te) may be used. The upper limit of e is not particularly limited', but if it is large, the operation is performed. It will become prosperous, so the quality is preferably 4 or less, more preferably 3 or less. The content ratio of the solution Tb towel (the monomer unit in the obtained polymer (P). The target composition of the ratio is the same 2 composition) and the expression of the early body α'η containing Τ1 39

201222146 —T\y^m KJ201222146 —T\y^m KJ

Te的各單體組成均與目標組成相同。 ，如’絲合物⑺是使單體χ、單^、單體 合而獲得的3元系的聚合物’且目標组成（莫耳二 以下相同）為广7，：2’時，使第2組成（莫耳％，以 同）X : y : ζ與X’ ： y’ ： Ζι相同。再者，實 目 ，所期望的效果方面，最佳為第2組成貫(=;二: (?耳%)相同’但若相對於該目標組成為爾的 摩巳圍内’較佳為±5%的範圍内的誤差，則被容許。即若 為1差範圍’則看作第2組成與目標喊相同。 溶液Tb是藉由滴加而供給至反應器中。 [溶液Sa] 溶液sa是主步驟中所使用的溶液S1、S2、 Sd (d ，1以上的整數）的總稱。作為溶液Sa，可僅使用i種溶 、文僅使用S1)’亦可使用2種以上的溶液（SbS2 Sd)。 d的上限值並無制限定，但若較多，則操作會變得繁璃， 因此實質上較佳為5以下，更佳為 4以下。 。。當使用2種以上的溶液作為溶液％時，溶液^中的 單體的含有比率（第1組成）是指S1〜Sd的合計的單體 的組忐。 口岭液S1〜溶液Sd各自的單體的組成彼此可相同，亦 可不同，且均與目標組成不同。第丨組成是單體屮〜單體 an^L中，共聚合反應速度最慢的單體的比例多於目標組成 的組成。第1組成中的該絲合反應速度最慢的單體的含 有比率（莫耳％)的值較佳為多於目標組成巾的該共聚合 201222146 ^uzoopif 反應速度最慢的單體的含有比率（莫耳％)的值的u倍。 較佳為溶液Sa中的單體的含有比率（第i組成）是參 考聚合物（P)中的目標組成與聚合中所使用的各單體的 反應性而事先求出的組成。 具體而言’較佳為溶液Sa的第i組成是以如下方式設 计的組成·若於反應器内所存在的單體的含有比率為第工 組成時向該反應器内滴加上述溶液Tb，則剛滴加之後所生 • 成的聚合物分子·的單體單元的含有比率成為與目標組成相 同。。於此情況下，由於剛滴加之後所生成的聚合物分子中 的單體單元的含有比率與所滴加的溶液Tb中的單體的含 有比率（目;f示組成）相同，因此剛滴加之後殘於 内的單體的含有比率始終成為固定（第i組成）。因此了若 向該反應器内継續滴加溶液Tb，則可獲得始終持續生成目 標組成的聚合物分子的穩定狀態。 、存在如可獲得該穩定狀態的第1組成是由本發明者等 首次獲得的發現。第1組成的設計方法將後述。 溶液Sa可事先加入至反應器内，亦可藉由滴加等而緩 慢地供給至反應器内，亦可將該些加以組合。 [聚合起始劑] 聚合起始劑是藉由滴加而供給至反應器内。可使溶液 Tb中含有聚合起始劑。當滴加溶液％時，亦可Each monomer composition of Te is the same as the target composition. For example, when the 'filament compound (7) is a ternary polymer obtained by combining a monomer oxime, a single monomer, and a monomer, and the target composition (the same applies to the following Mohs), the width is 7, 2', and the 2 composition (mole%, same) X: y: ζ is the same as X': y': Ζι. Furthermore, in terms of the actual effect, the desired effect is preferably the second component (=; two: (the ear %) is the same 'but preferably within ± 相对 相对 相对 相对 相对The error within the range of 5% is allowed, that is, if it is the range of 1 difference, the second composition is regarded as the same as the target. The solution Tb is supplied to the reactor by dropping. [Solution Sa] Solution sa It is a general term for the solutions S1, S2, and Sd (d, an integer of 1 or more) used in the main step. As the solution Sa, only one type of solution can be used, and only two types of solutions can be used. SbS2 Sd). The upper limit of d is not limited, but if it is large, the operation becomes fine, and therefore it is preferably 5 or less, more preferably 4 or less. . . When two or more kinds of solutions are used as the solution %, the content ratio (first composition) of the monomers in the solution is the group 单体 of the total of the monomers S1 to Sd. The compositions of the respective monomers of the sulphate liquid S1 to the solution Sd may be the same or different, and are different from the target composition. The composition of the third unit is monomer 屮 ~ monomer an ^ L, the proportion of the monomer with the slowest copolymerization reaction is more than the composition of the target composition. The content ratio (mol%) of the monomer having the slowest reaction speed in the first composition is preferably more than the content ratio of the monomer having the slowest reaction rate of the copolymerization 201222146 ^uzoopif of the target composition. U times the value of (mole%). The content ratio (i-th composition) of the monomer in the solution Sa is preferably a composition obtained in advance by referring to the reactivity of the target composition in the polymer (P) with each monomer used in the polymerization. Specifically, it is preferable that the ith composition of the solution Sa is a composition designed as follows. If the content ratio of the monomer present in the reactor is the first component, the above solution Tb is added dropwise to the reactor. The content ratio of the monomer unit of the polymer molecule formed immediately after the dropwise addition is the same as the target composition. . In this case, since the content ratio of the monomer unit in the polymer molecule formed immediately after the dropwise addition is the same as the content ratio of the monomer in the dropwise added solution Tb (the composition of f; The content ratio of the monomer remaining after the addition is always fixed (the i-th composition). Therefore, if the solution Tb is successively dropped into the reactor, a stable state of the polymer molecules which continuously maintain the target composition can be obtained. The first component in which the stable state is obtained is the first discovery obtained by the inventors of the present invention. The design method of the first composition will be described later. The solution Sa may be added to the reactor in advance, or may be slowly supplied to the reactor by dropping or the like, or may be combined. [Polymerization Initiator] The polymerization initiator was supplied to the reactor by dropwise addition. The polymerization initiator can be contained in the solution Tb. When the solution is added dropwise, it can also

Sa中含有聚合起始劑。亦可使所滴加的2種以上的溶液（“ 及/或Tb)中含有聚合起始劑。亦可與溶液％、溶液孔 分開來滴加含有聚合起始劑的溶液（聚合起始劑溶液）。亦 201222146 可將該些加以組合。 主步驟中的聚合起始劑的使用量（主步驟 量）是對應於聚合起始劑的麵、且對應於 二仏給 物（P)的重量平均分子量的目標值而設定。均的聚合 例如，當本實施形態中的聚合物（p)為微 共聚合物時’相對於主步驟t向反應器内供給的 計（主步驟中的總供給量）的100莫耳％，聚合 使用量（主步驟中的總供給量）較佳為i莫耳0/ Qj的 %的範圍，更佳為1.5莫耳％〜2G莫耳％的範圍。、耳Sa contains a polymerization initiator. It is also possible to contain a polymerization initiator in two or more kinds of solutions ("and/or Tb") which are added dropwise. A solution containing a polymerization initiator (polymerization initiator) may be added dropwise separately from the solution % and the solution pores. The solution may be combined. The amount of the polymerization initiator used in the main step (the main step amount) is the surface corresponding to the polymerization initiator and corresponds to the weight of the diterpene (P). The average molecular weight is set as the target value. For example, when the polymer (p) in the present embodiment is a micro-copolymer, the meter is supplied to the reactor in the main step t (the total supply in the main step) The amount of polymerization (the total amount of supply in the main step) is preferably in the range of % of i mol 0 / Qj, more preferably in the range of 1.5 mol % to 2 G mol %. ear

[溶液Sa中的單體的含量] W 聚合步驟巾所使㈣單體的合計量（總單體供 ，液Sa、溶液Tb、溶液Uc中所含的單體的總二= 應於欲獲得的聚合物（ρ)的量而設定。 另外，若該總單體供給量之中，溶液Sa中所 體的合計量所佔的_過少，缝法充分賴得^用Γ 液sa所產生騎期望的效果，若過多，則於聚合步 合物的分子量變得過高。因此，相對於總| λ 體iw。里，浴液Sa中所含有的單體的合計量較佳為s · %〜40質量％，更佳為5質量0/〇〜3〇質量％。 里 [溶液Sa、溶液孔的供給] 於主步驟中，當向反應器内滴加聚合起始劑時，該反 應器内^需存在溶液Sa。因此，於向反應器内滴加聚合起 始劑之刖、或與開始滴加聚合起始劑的同時，向該反應器 内開始供給溶液Sa。 。° 42 201222146 πυζδδριί 需存在溶液5= t液㈣，該反應器内必 後、或與開始供給溶液開始供給溶液Sa之 溶液刊。較佳為溶液Tb的°、向5亥反應益内開始滴加 滴加開始為同時、或於始與上述聚合起始劑的 較佳為聚合起始劑二劑的滴加開始之後。 為同時。於溶液Tb的滴加 1 力的滴加開始[Content of the monomer in the solution Sa] W The total amount of the monomers (the total monomer supply, the liquid Sa, the solution Tb, and the monomer contained in the solution Uc) is determined by the polymerization step towel. In addition, if the total amount of the monomer is supplied, the total amount of the body in the solution Sa is too small, and the sewing method is sufficiently dependent on the riding of the liquid sa. If the effect is too large, the molecular weight of the polymerization step becomes too high. Therefore, the total amount of the monomers contained in the bath Sa is preferably s · % with respect to the total | λ body iw. ～40% by mass, more preferably 5 mass%/〇3〇质量%. [Solution Sa, supply of solution pores] In the main step, when a polymerization initiator is added dropwise to the reactor, the reactor The solution Sa is required to be present. Therefore, the supply of the solution Sa is started in the reactor while the polymerization initiator is added dropwise to the reactor or the start of the dropwise addition of the polymerization initiator. ° 42 201222146 πυζδδριί The solution 5 = t liquid (4) is required to be present, and the solution of the supply solution Sa is started after the reactor or the start of the supply of the solution. Preferably, the dropwise addition of the solution Tb to the start of the dropwise addition to the reaction of 5 liters starts simultaneously, or after the start of the dropwise addition of the polymerization initiator of the above polymerization initiator, preferably. Start with the addition of 1 force to the solution Tb.

、玄饬TU ^ * 、'，°束之刖結束溶液Sa的供給。 吟液Tb的滴加可連續地滴加， 加速度可變化。為了使所生成 ^門，地滴加，滴 穩定’較佳為以固定速度連續地二。纽力子量更 歇地、1加來供給溶液^時，可連續地滴加，亦可間 成及敎，較佳為以岐速度連tit ▲:液Sa較佳為於聚合步驟的初期供給其全量。且體而 i止劑的滴加開始至溶液Tb的滴力:結束 二Γί 較佳為於經過該基準時間的鳳以 束溶液％的供給。例如於基準時間為4小時的情況 兑，車乂佳為於自聚合起始劑的滴加開始算起經過48分鐘以 刖，將溶液Sa的全量供給至反應器内。 佳為躲麟練料基準軸的15%时，更 另外’亦可於基準時間的0%的時間點供給溶液^的 全量。即，亦可於聚合起始劑的滴加開始前，預先將溶液 Sa的全量加入至反應器内。 43 201222146 [聚合起始劑的供給速度] ::驟中的聚合起始劑的滴加可進行至溶液几的滴 止’亦可於溶液Tb的滴加結束前結束。較佳 為進仃至溶液Tb的滴加結束時為止。 聚合起始劑的供給速度可為固定，尤其，藉由 的供給量，可抑制聚合初期的高分“成分 得二二φ的生成其結果’可減少結束聚合步驟而獲 提曰t子量的偏差。該分子量的均-化有助於 於Ls，程用聚合物對於抗㈣j用溶劑的溶解性或對於 =性4液的溶解性，且有助於提昇抗_組成物的感光 储平iv·! V驟的初期所生成的聚合物的重量平均分子量根 ^ 4細期的聚合起始_供給量而變化。因此， 劑的最佳的供給速度雖然亦根據單體的種類、單 速度、聚合起始劑的種類、聚合條料而不同， =佳為以使聚合步驟的初期所生成的聚合物的重量平均 刀子量接近目標值的方式設定。 义具體而言，較佳為於經過上述基準時間的5%〜2〇%以 階段’供給主步驟中所使用的聚合起始劑的總供 =、30%〜90%，其後以低於該初細段的速度供給聚 該初期階段較佳為上述基準時間的55%〜175%，更 ，為6%〜15%。該初期階段的聚合起始劑的供給量更佳為 γ驟中所使用的聚合起始劑的總供給量的35質量％〜 44 201222146 H-W^ooplf 85質量％，進而更佳為40質量％〜80質量0/〇。 [主步驟的較佳的形態] ()作為主步驟的較佳的形態，可列舉以下的（a)、（b) (a)事先向反應n内加人以第丨組成含 二、、^為容^ S3，量（S1)，將反應器内加熱至規定的 聚…皿度為止後’向該反應器内分別 =的, Xuanzang TU ^ *, ', ° bundle of 刖 end of the supply of solution Sa. The dropping of the sputum Tb can be continuously dropped, and the acceleration can be varied. In order to make the generated gate, the ground drop, the drop stability ' is preferably two consecutively at a constant speed. When the amount of the force is more intermittent, and the solution is supplied to the solution, the mixture may be continuously added dropwise or may be formed into a mixture. Preferably, the tantalum is connected at a speed of 岐: the liquid Sa is preferably supplied at the initial stage of the polymerization step. Its full amount. Further, the dropping of the stopper starts to the dropping force of the solution Tb: the end is preferably supplied to the phoenix solution after the reference time. For example, in the case where the reference time is 4 hours, it is preferable to supply the entire amount of the solution Sa to the reactor after 48 minutes from the start of the dropwise addition of the polymerization initiator. When the best value is 15% of the reference axis of the nucleus, the total amount of the solution ^ can be supplied at the time of 0% of the reference time. That is, the entire amount of the solution Sa may be previously added to the reactor before the start of the dropwise addition of the polymerization initiator. 43 201222146 [Supply rate of polymerization initiator]: The dropwise addition of the polymerization initiator in the step may be carried out until a few drops of the solution may be completed before the completion of the dropwise addition of the solution Tb. It is preferred to carry out the dropwise addition until the end of the dropwise addition of the solution Tb. The supply rate of the polymerization initiator can be fixed. In particular, by the supply amount, it is possible to suppress the high score at the initial stage of polymerization, and the result of the formation of the two components φ can reduce the amount of enthalpy of the end of the polymerization step. Deviation. The homogenization of the molecular weight contributes to the solubility of Ls, the polymer for the solvent, or the solubility of the liquid, and contributes to the improvement of the photosensitive storage of the anti-composition. · The weight average molecular weight of the polymer produced in the initial stage of the V step varies depending on the polymerization start_supply amount of the fine phase. Therefore, the optimum supply rate of the agent depends on the type of the monomer, the single speed, The type of the polymerization initiator is different depending on the type of the polymerization initiator, and it is preferably set such that the weight average knife amount of the polymer produced in the initial stage of the polymerization step is close to the target value. 5% to 2% of the reference time is supplied to the total supply of the polymerization initiator used in the main step = 30% to 90%, and then supplied at a rate lower than the initial stage. Preferably, it is 55% to 175% of the above reference time, more It is 6% to 15%. The supply amount of the polymerization initiator in the initial stage is more preferably 35 mass% of the total supply amount of the polymerization initiator used in the gamma step - 44 201222146 HW^ooplf 85 mass%, and further More preferably, it is 40 mass% - 80 mass / 〇. [Preferred form of main process] () As a preferable aspect of a main process, the following (a), (b) (a) n In addition, the composition of the second group contains the second, the ^ is the capacity ^ S3, the amount (S1), the reactor is heated to the specified poly degree ... after the 'into the reactor respectively =

彳的-部分的聚合起始劑==所2 、.且成含有單體αι〜單體αη、且含有聚 及乂第2 的溶液Tb。聚合起始劑溶液與溶液τ:分 或先開始滴加聚合起始劑溶液。較佳為=時=二 ==一的滴加開始為止 液加速度㈣私起始液先於溶 僅向反應H内加人溶劑，加熱至規定的聚合溫度 ^後，分別滴加以第1組成含有單體％〜單體％、且含 ^步驟中所供給的聚合起始躺—部分的溶液^，及以 第2組成含有單體αι〜單體〜、X含有該聚合起始劑的剩 餘部分的溶液Tb。兩液是__滴加、絲開始滴加溶 液Sa。自溶液Sa的滴加開始至溶液Tb的滴加開始為止的 時間較佳為0分鐘〜10分鐘。 較佳為滴加速度分別為固定。溶液Sa先於溶液Tb結 束滴加。 45 201222146 (c)事先向反應器内加入湓该^ 器内加熱至規定的聚a，A &amp;的—部分，將反應 加將主步财㈣反應11时別滴 部分），及以第2組成含有單體α〜j^為，合液以的剩餘 起始劑的剩餘部分的溶液Tb液早含有聚合 較佳為nt Λ先開始滴加溶液Sa的剩餘部分。 =為问時。自溶液Sa的剩餘部分的滴 的滴加開始為止的時間較佳為G分鐘〜1G分鐘。-液Tb 溶液==：^分咖定。娜的_分先於 &lt;溶液Sa的第1組成的設計方法〉 以下’對第1組成的較麵設財 藉由下述方法（1)〜方法r4、七b„ 的含有比率）S,a。 法⑷’求出早體組成（單體 當欲獲得㈣合物（P)巾的單料元的含有 組成，單位：莫耳Q/ )為， ，. „ .早斗0Mu...:&lt;時，若以α&quot;:The hydrazine-partial polymerization initiator == 2, and the solution Tb containing the monomer α1 to the monomer αη and containing the poly(p) and the second. The polymerization initiator solution is mixed with the solution τ: or the polymerization initiator solution is initially added dropwise. Preferably, the liquid acceleration is started at the beginning of the addition of =======. The private starting liquid is added to the reaction H before the solvent is added to the reaction H, and heated to a predetermined polymerization temperature, and then the first component is added dropwise. a monomer % to monomer %, and a solution containing the polymerization start-up portion supplied in the step, and a second component containing the monomer α1 to monomer ~, X containing the remainder of the polymerization initiator Solution Tb. The two liquids are __ dripping, and the silk starts to drip the solution Sa. The time from the start of the dropwise addition of the solution Sa to the start of the dropwise addition of the solution Tb is preferably from 0 minutes to 10 minutes. Preferably, the drop acceleration is fixed. The solution Sa was added dropwise before the solution Tb. 45 201222146 (c) Add to the reactor in advance, heat the furnace to the specified poly a, A &amp; part, add the reaction to the main step (four) reaction 11 when the drop part), and the second The solution Tb containing the remainder of the remaining initiator of the mixture containing the monomers α~j^ is contained in the solution, and the remainder of the solution Sa is preferably started to be polymerized, preferably nt. = for question. The time from the start of the dropwise addition of the dropwise portion of the solution Sa is preferably from G minutes to 1 G minutes. - Liquid Tb solution ==:^ is divided into coffee. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ a. Method (4) 'To determine the composition of the early body (the monomer contains the composition of the single element of the (4) compound (P) towel, the unit: Moer Q / ) is, ,. „ .早斗0Mu... :&lt;, if you use α&quot;:

αυαΐη表示S，a的組成（單位：莫耳％)， F =藉由—下述⑴〜—下述⑶的方法所求出的因數，則n 〇又為 au —αι/Fi、a12 = a'2/F2、…ain=：ain/Fn。 較佳為溶液Sa的第[組成中的各單體^含有 為S’a中的各單體的含有比率的值的〇 8倍〜i 2 内，更佳為0.9倍〜U倍的範圍内，進而更佳為°〇95倍 〜1.05倍的範圍内。 46 201222146 H^uzoopif (1) 首先，以固定的滴加速度，將含有單體組成與目 標組成: α'2 :…：α'η相同的單體混合物1〇〇質量份、 聚合起始劑、及溶劑的滴加溶液滴加至僅加入有溶劑的反 應器内，當自滴加開始算起的經過時間為tl、t2、.時， 求出为別殘存於反應器内的早體〜單體％的組成（單 位：莫耳％) : M2:…：Mn，及自tjt2為止的期間、 自h至h為止的期間、…内分別生成的聚合物中的單體單 元吣〜單體單元α，η的比率（單位：莫耳％) ^ : p2: ·Υααΐη represents the composition of S,a (unit: mole%), F = factor obtained by the method of (1) to (3) below, then n 〇 is again au —αι/Fi, a12 = a '2/F2,...ain=:ain/Fn. It is preferable that each monomer in the composition [the composition of the solution Sa is in the range of 〇8 times to i 2 of the content ratio of each monomer in S'a, more preferably in the range of 0.9 times to U times. Further preferably, it is within a range of 95 〜 to 1.05 times. 46 201222146 H^uzoopif (1) First, at a fixed drip rate, a monomer mixture having the same monomer composition and target composition: α'2 :...:α'η, 1 part by mass, a polymerization initiator, And the dropwise addition solution of the solvent is added dropwise to the reactor in which only the solvent is added, and when the elapsed time from the start of the dropwise addition is t1, t2., it is determined that the precursor is not left in the reactor. The composition of the % by volume (unit: % by mole): M2: ...: Mn, and the period from tjt2, the period from h to h, the monomer unit in the polymer generated in ..., the monomer unit Ratio of α, η (unit: mol %) ^ : p2:

Pn。 2 …· (2) 找出上述Pl:p2:…：匕最接近目標組成 α’2 :…：（χ’η的時段「自^至Wi為止的期間（m為i以 上的整數）」。 (3 )根據S亥「自屯至tm+ 1為止的期間」内的: :.Pn. 2 (2) Find out that the above Pl:p2:...:匕 is closest to the target composition α'2 :...: (the period of χ'η "the period from ^ to Wi (m is an integer greater than i)". (3) According to S Hai's "Period from t屯 to tm+ 1": :.

Pn的值、及經過時間tm内的Ml ·· M2 :…·· Mn的值，藉由 下述式而求出因數Fl、F2、.々Fi = Pi/Mi、F2=p \ = Pn/Mn。 …n (4)若以αι1 ·叫：：αΐη表示s,a的組成（單位： 莫耳/〇) WFi F2、…Fn表示上述（3)中所求出的因數， 則 α^ — α^、a12 = a'2/F2、...0^= a'n/Fn。 若更具體地進行說明，關如當聚η合物（P)是使單 體X、單體y、單體z進行共聚合而獲得的3元系的聚合物， 且目標組成為x，：y，：z，時，將S，a的組成（莫耳％，以下 相同）X⑻：yQQ: ZGQ設為使用以下述方法求出的因數&amp;、 因數 Fy、因數 Fz 賴由 x〇〇==xVFx、y〇〇 = y，/Fy、z〇〇 = zVFz 47 201222146 所算出的值。 [因數Fx、因數Fy、因數Fz的求法] 以下，列舉聚合物（P)是3元系的聚合物的情況為 例進行說明，⑬即便為2元系或4元系以上，亦能夠以相 同方式求出因數。 (1)首先，以固定的滴加速度v，將含有單體組成與 目標組成X’ ： y’ ： Z，相同的單體混合物、溶劑、及聚合起始 劑的滴加溶液滴加至反應器内。反應器内事先僅加入 劑。 ^ 分別===起的經過時間為、t2、‘.時，求! it ΐ /的單體x、單體y、單體z的組成（: 為：的期x門y.::，及自…2為止的期間、“至 ，「自V mPy.Ρζ最接近目標組成x’:y，:ζ，的1 P :寺該自、至砧+1為止的期間」内的Px:Py 二時間U内的MX··岣:心，藉由 述式而求出因㈣、因數Fy、因數&amp;的值The value of Pn and the value of Ml ·· M2 :...·· Mn in the elapsed time tm are obtained by the following equations: F1, F2, .々Fi = Pi/Mi, F2=p \ = Pn/ Mn. ...n (4) If α1 is called α1, 叫::αΐη represents the composition of s, a (unit: moor/〇) WFi F2, ... Fn represents the factor obtained in (3) above, then α^ — α^ , a12 = a'2/F2, ...0^= a'n/Fn. More specifically, when the poly(N) complex (P) is a ternary polymer obtained by copolymerizing the monomer X, the monomer y, and the monomer z, and the target composition is x, y,:z, the composition of S, a (mol%, the same below) X(8): yQQ: ZGQ is set to use the factor &amp; factor Fy, factor Fz obtained by the following method depends on x〇〇= =xVFx, y〇〇= y, /Fy, z〇〇= zVFz 47 201222146 Calculated value. [Factor Fx, Factor Fy, Factor Fz] Hereinafter, a case where the polymer (P) is a ternary polymer will be described as an example, and 13 may be the same even if it is a ternary system or a quaternary system or more. The way to find the factor. (1) First, a dropping solution containing a monomer composition and a target composition X': y': Z, the same monomer mixture, a solvent, and a polymerization initiator is added dropwise to the reactor at a fixed dropping velocity v Inside. Only the agent was added in advance in the reactor. ^ The elapsed time from === respectively, when t2, '., find the composition of monomer x, monomer y, and monomer z of it ΐ / (: is the period x gate y.::, and Px: Py in the period from the time of the period of the period of the period of the period of the period of the period of the period of the period of the period of the period of the period of MX··岣: in the time U, the value of (4), factor Fy, factor &amp;

Fx = Px/Mx、Fx = Px/Mx,

Fy ~~ Ρ^/1νιΥ ' Fz = Pz/Mz 因數Fx、因邀 P _ ^ 應性的值，^科因數FZ歧映各單_相對的反 氟合的早體的組合或目標組成改變，則 48 201222146 πυζΰδριί 因數Fx、因數Fy、因數Fz會變化。 z〇〇是使用因數 y〇〇 = yVFy , z〇〇 (4) S，a的組成（莫耳％) χ⑻：y〇〇: Fx、因數 Fy、因數 Fz，藉由 x〇〇 = x，/Fx、 =z'/Fz而算出的值。 &quot;且:Ϊ實St，當使用上述因數來設計溶仏的第 1、、且成時，於獲仵所期望的效果方面，較佳 第 的組成為·%的範圍内，更佳為_%的範圍内，^^ 佳為±5%的範_的誤差，最佳為第i = 土 S，a (莫耳％)相同。 又V吴斗/0)與 &lt;後步驟&gt; 於後步驟中，向主步驟已結束的反應H㈣加溶液 [溶液Uc] 溶液Uc是後步驟中所使用的溶液m、幻、 上的紐）的總稱。作為溶液UC，可僅使用1種溶 f(僅使用叫亦可制2種以上的溶液㈤、U2...Uf)t 的艮值並無特別限定，但若較多，則操作會變得繁項， 因此實質上較佳為5以下，更佳為4以下。 當使用2種以上的溶液作為溶 單體的含有比率（第3組成）是指 的組成。 液Uc時’溶液Uc中的 U1〜Uf的合計的單體 /谷液U1〜溶液Uf各自的單體的組成彼此可相同，亦 可不同’且均與目標組成不同。第3組成是單體α1〜單體 αη之中，纟聚合反應速度最慢的單體的比例少於目標組成 49 201222146 的組成 有比率二合反應速度最慢的單體的含 應速度最,_單_含扣率（該共聚合反 ，丨、击从从， 、关斗/〇)的值的0.9倍還 知更佳极α7倍射。第3組成 度最慢的單體的含有比率亦可為〇。 〜ϋ應速Fy ~~ Ρ^/1νιΥ ' Fz = Pz/Mz factor Fx, due to the value of P _ ^, ^F factor FZ disambiguation of each single _ relative anti-fluorinated early body combination or target composition change, Then 48 201222146 πυζΰδριί The factor Fx, the factor Fy, and the factor Fz change. Z〇〇 is the composition of the factor y〇〇= yVFy , z〇〇(4) S,a (mole%) χ(8):y〇〇: Fx, factor Fy, factor Fz, by x〇〇= x, The value calculated by /Fx, =z'/Fz. &quot;And: Ϊ St, when using the above factors to design the first, and the time of dissolution, in terms of the desired effect of the enthalpy, the preferred composition is in the range of %, more preferably _ Within the range of %, ^^ is preferably ±5% of the error of _, preferably the same as i = soil S, a (mole %). Further V Wudou/0) and &lt;post-step&gt; In the subsequent step, the solution to the end of the main step H (four) is added [solution Uc] solution Uc is the solution used in the subsequent step m, magic, on the new The general name of ). As the solution UC, the enthalpy value of only one type of solution f (only two or more types of solutions (5), U2, ... Uf) can be used, and the enthalpy value is not particularly limited, but if it is large, the operation becomes In general, it is preferably 5 or less, more preferably 4 or less. When two or more kinds of solutions are used as the content ratio of the solvent (third composition), it means a composition. In the case of the liquid Uc, the total monomer of U1 to Uf in the solution Uc/the composition of the monomer of the solution U1 to Uf may be the same or different from each other and may be different from the target composition. The third composition is that among the monomers α1 to αα, the proportion of the monomer having the slowest polymerization rate of ruthenium is less than the target composition 49 201222146. The composition of the monomer having the slowest reaction rate is the slowest. The _ single_ buckle rate (the total of the copolymerization, 丨, 从 from,, 关 / 〇) is also 0.9 times better than the value of α7 times. The content ratio of the monomer having the slowest third composition may also be ruthenium. ~ϋ应速

溶液Ue帽含料體的合計量為聚合步财所使用 H給量的W f量％〜1G f量％，較佳為G.1質量 曰^7.5質篁。/。，更佳為αι質量％〜5質量％。若為μ質 Κ以上，則容緖得藉由設置後步驟帶來的充分的效果。 若為10質量％以下、或7.5質量％以下、或5質、 以下’則容易充分地獲得減少聚合物組成的偏差的效^。° &lt;溶液Uc的第3組成的設計方法&gt; 溶液Uc中的單體的組成（第3組成） 述方法⑸〜方法⑻而求出單體組成（單體$ = 率）U’c，並根據該u，c進行設計的組成。 U’c的組成除將上述第丨組成的設計方法中的因數The total amount of the Ue cap-containing material in the solution is the amount of W f % to 1 G f % of the amount of H supplied by the polymerization step, preferably G.1 mass 曰 ^ 7.5 mass 篁. /. More preferably, it is αι% by mass to 5% by mass. If it is above μ quality, it will have sufficient effect by setting the post step. When it is 10% by mass or less, or 7.5% by mass or less, or 5 or less, it is easy to sufficiently reduce the variation in polymer composition. ° &lt;Design Method of Third Composition of Solution Uc&gt; Composition of Monomer in Solution Uc (Third Composition) The monomer composition (monomer $= rate) U'c is determined by the methods (5) to (8). And according to the u, c design composition. The composition of U'c is in addition to the factor in the design method of the above-mentioned 丨

〜FJ中的最小者替換為0以外，使用相同因數，1 以下的方法而求出。 由 〇〇即，當表示欲獲得的聚合物（P)中的單體單元吣〜 單體單元α’η的含有比率的目標組成（單位：莫耳％)為. α’2: : α'η 時，若以 α3ΐ : α32:…：α3η 表示 U'C 的組成 位：莫耳％)，aFl、F2、…Fn (其中，將匕〜匕中的最小 者替換為0)表示由下述（5)〜下述（7)的方法所求出 的因數，則設為 a31 = ( ο^χΐ^ + α'2χ；ρ2 + 50 201222146 H-UZOOpif «nXFJ . «32 = α·2χρ2/ (a.xFl + a，xF2+} ^ = a-xFn/(a^F1 + aW2+... + a.xF)o …' 別仏的第3域切各賴的含有比率分 =為Uc中的各単體的含有比率的值的 圍内，更佳為0.9倍〜】M立的浐圏向A 2饴的靶 倍〜⑽倍的範圍内。的範圍内，進而更佳為〇.95 (#^Vluncr. 第?Si (莫耳%)。於獲得所期望的效果方面， 。/、、的該共聚合反應速度最慢的單體的組成（莫耳 〇佳為1G莫耳％町，更佳為5莫耳％以下，最佳為 …方法⑸〜方法⑺與上述第1組成的 叹5十方法中的方法⑴〜方法⑴相同。 關 …(:)J先，以固定的滴加速度，將含有單體組成與上 二iifal:a’2:...:a’n相同的單體混合物刚質量 二^_滴加溶液滴加至僅加入有溶劑 砗=，虽自滴加開始算起的經過時間 時’求出分別殘存於反應器⑽單體 (單位:物m:M2:…··Μη，及自 間、自t2至t3為止的期間、…分 :、 p體單元a,〜單體單元心的比率(單的單 ⑷找出上述^:…：匕最接近目標 I的時段「自^至一為止的期間(丄1以 51 201222146 -rv厶 ο opif 上的整數）」。 ⑺根據《•亥自、至屯+1為止的期間」内的P1:P2:. Pn的值、及經過時間tm内的Ml: M2: : Mn的值藉由 下述式而求出因數 = Pn/Mn。 .· n (8)若以《31 . ot32 :…：α3η表示w的組成（單位··The smallest one of the ~FJ is replaced by 0, and is obtained by the same factor and a method of 1 or less. The target composition (unit: mol %) of the content ratio of the monomer unit 吣 to the monomer unit α' η in the polymer (P) to be obtained is α.2: : α' In the case of η, if α3ΐ : α32:...:α3η represents the composition bit of U'C: mol%), aFl, F2, ... Fn (where the smallest of 匕~匕 is replaced by 0) is represented by the following (5) ~ The factor obtained by the method of (7) below is set to a31 = ( ο^χΐ^ + α'2χ; ρ2 + 50 201222146 H-UZOOpif «nXFJ . «32 = α·2χρ2/ ( a.xFl + a,xF2+} ^ = a-xFn/(a^F1 + aW2+... + a.xF)o ...' The ratio of the content ratio of the carcass is preferably 0.9 times to 5% of the range of the target of the A 2 饴 to the range of (10) times, and more preferably 〇.95 (# ^Vluncr. No. Si (mole%). In terms of obtaining the desired effect, the composition of the monomer having the slowest copolymerization rate is the lowest (1% molar). Good for 5 mA% or less, the best for... Method (5) ~ Method (7) with the above composition 1 sigh 5 The method (1) ~ method (1) in the method is the same. Off... (:) J first, with a fixed drop rate, the monomer mixture containing the same monomer composition as the above two iifal:a'2:...:a'n Just after the mass two ^_ dropwise addition solution is added to the solvent only 砗 =, although the elapsed time from the start of the dropwise addition 'determine the residual monomer in the reactor (10) (unit: m: M2: ... Μη, and the period from t2 to t3, ... points:, p body unit a, ~ unit cell ratio (single sheet (4) find the above ^:...: 匕 closest to the target I period "The period from ^ to one (丄1 is an integer on 51 201222146 -rv厶ο opif)". (7) The value of P1:P2:. Pn in the period from "•海自至至屯+1" And the value of Ml: M2: : Mn in the elapsed time tm is obtained by the following formula: Factor = Pn / Mn. . . . (n) If "31. ot32 :...:α3η represents the composition of w ( unit··

莫耳。/。），以Fl、F2、...Fn(其中’將Fi〜Fn中的最小者替 換為0)表π上述（7)中所求出的因數，貝j α3ΐ==α (a，lXFl + a，2xF2 + ... + a，nXFn )、％ = A，（ + a，2xF2 + …+ a，nxFn)、..·α3η= a，nXFn/ ( 一匕 + 吣％ + . + a'nxFn) 〇 ’·· 於本實施贿巾，當使紅述因數來設計溶液u 早體的組成（第3組成）時，於獲得所期望的效果方面， 較佳為相對於U，e的域為·%的範 的範圍内，進而更料±5%的翻_誤差，H = 組成與S，a (莫耳％)相同。 雜為第3Moor. /. ), with Fl, F2, ... Fn (where 'the smallest of Fi~Fn is replaced by 0) table π the factor obtained in (7) above, Bay j α3 ΐ == α (a, lXFl + a, 2xF2 + ... + a, nXFn ), % = A, ( + a, 2xF2 + ... + a, nxFn), .. · α3η = a, nXFn / ( 一匕 + 吣% + . + a' nxFn) 〇'·· In the present implementation of the bribe towel, when the composition of the solution u early body (the third composition) is made by the redness factor, it is preferable to obtain the desired effect with respect to the domain of U, e. Within the range of %, and thus ±5% of the error, the composition of H = is the same as S, a (% of Mo). Miscellaneous for the third

組射職共聚合反應速度最慢的單體的 下S5較佳為1〇莫耳%以下，更佳為5莫耳%以 溶液Uc較佳為於溶液Tb的滴加結束後立即開始滴 加0 溶液Uc的滴加讦連續地供給U1 ’亦可依次（間歇地） 供給U〗、U2...Uf。滴加速度可變化。亦可同時供給w、 U2...Uf中的2種以J：^較佳為伴隨時間的經過，藉:溶液 52 201222146The lower S5 of the group having the slowest rate of co-polymerization reaction is preferably 1 〇 mol% or less, more preferably 5 mol%, and the solution Uc is preferably added dropwise immediately after the completion of the dropwise addition of the solution Tb. 0 The dropwise addition of the solution Uc is continuously supplied to U1', and U, U2, ... Uf may be supplied sequentially (intermittently). The drop acceleration can vary. It is also possible to supply two kinds of w, U2...Uf at the same time, and J:^ is preferably accompanied by the passage of time, by: solution 52 201222146

Uc的滴加而向反應器内供給的每單位時間的單體的供給 ! (m、U2...Uf中的單體的合計量）逐漸、或階段性地 減少。The supply of the monomer per unit time supplied to the reactor by the dropwise addition of Uc ! (the total amount of the monomers in m, U2, Uf) is gradually or stepwisely reduced.

例如，使用單體組成及單體的含量（濃度）全部均一 的1種洛液（U1)作為溶液Uc，可使滴加速度連續地減 ：&gt;'，亦可使滴加速度階段性地減少。或者，亦可使用單體 組成彼此相同（上述誤差範圍被容許），但單體的含量（濃 度）互不相同的2種以上的溶液（U卜U2 Uf)作為溶液 Uc。於此情況下，即便滴加速度固定，藉由以單體的濃度 減少的方式依次滴加2種以上的溶液，亦可逐漸、或階= 性地減少每單位時間的單體的供給。 又 具體而言，當將自溶液Uc的滴加開始至滴加結束肩 止作為後滴加時間，將後步财的單體的總供給量除以稽 5時間所得·作為平均供給速度時，較料將自後消 0%至k% (k為5〜95)為止的期間作為以㈣ ^ 2供、、、S速度更尚的速度供給單體的高速供給期間，於錢 :速供給期間内將後步驟$的單體的總供給量中的％督 置％〜95質量％供給至反應器内。 該k更佳為2G%〜8G%，進而更佳為规〜观。於 供給期_供給至反應糾的單體更佳為後步驟 /υ貝罝〇/〇〜85質量％。 器 於後步驟中，當向反應n内滴加溶液Ue _，該反麻 内必需存在聚合起始劑。因此’較佳為於後步驟中亦^ 53 201222146 反應器内供給聚合起始劑。 可使溶液Uc中含有聚合起始劑，亦可與溶液Uc分開 來滴加含有聚合起始劑的溶液（聚合起始劑溶液）。f 該些加以組合。 例如，當本實施形態中的聚合物（P)為微影製程用 聚合物時，相對於後步驟中供給至反應器内的單體的合 (後主步驟中的單體的總供給量）的100莫耳％，聚:起 始劑的使用量（後步驟中的聚合起始劑的總供給量）較佳 為1莫耳％〜25莫耳％的範圍，更佳為1.5莫耳％〜20草 耳％的範圍。 、 於後步驟結束後，即溶液Uc的滴加結束後，視需要 可適且進行將反應器内保持成聚合溫度的保持步、 步驟、精製步驟等。 V郃 根據本發明者等的發現，於滴加聚合中，當僅將單體 組成與目標組成相同的單體溶液連續地滴加至反應器内 夺1&amp;剛開始之後所生成的聚合物中的單體單元的含有 比^與目標域的差較大，伴隨咖雜過而逐漸地接近 目才$、、且成，但若於單體溶液的滴加結束後進入至保持步 驟，則所生朗聚合物巾的單料元的含有比率與目標組 成的差逐漸地變大。具體而言，保持步驟中的經過時間越 長’自=生成的聚合物中的共聚合反應速度最慢的單體衍 ΐ出的單體單元的組成比越顯著地變大。由此可認為，當 ^體二液的滴加結束時，於反應器内’共聚合反應速度最 k的單體相對於目標喊而過剩地殘留。 54 201222146 -τν/^οομίΐ 、本貝施u ’首先於主步驟中，藉由使用以可獲得 上述穩定狀態的方式來設計單體的含有比率的溶液Sa與 溶液Tb，而自剛開始聚合反應之後生成與目標組成大致相 同組成的聚合物分子，且該狀態得以持續。因此，主步驟 中所生成的聚σ物成為單體單元的含有比率的偏差減少 者。 另外’於主步驟之後’設置不進行保持步驟，而直接 φ :商加共聚合反應速度最慢的單體的比例少於目標組成的溶 液UC的後γ驟，並以多於目標組成的比例向反應器内供 給共聚合反應速度最慢的賴料的單體。較佳為溶液Uc 不含共聚合反應速度最慢的單體，於後步驟中僅供給共聚 合反應速度最慢的單體以外的單體。 藉此，於溶液Tb的滴加結束時的反應器内，一邊高 效f地消耗相對於目標組成而過剩地殘留的共聚合反應速 度最杈的單體，一邊生成聚合物，因此防止主步驟後所生 成的聚合物中的單體單元的含有比率與目標組成的差隨時 ⑩ 間經過而變大。因此’可減少最終所獲得的聚合物（p) 中的單體單元的含有比率的偏差。 另外’藉由將溶液Uc的單體組成設為以使用上述因 數的設計方法所獲得的組成u，c ’可使主步驟後所生成的 聚合物中的單體單元的含有比率更接近目標組成。 〇〇進而’於後步驟中，使藉由溶液Uc的滴加而供給的 單，（較佳為僅是共聚合反應速度最慢的單體以外的單體） 的每單位時間的供給量隨時間經過而減少，藉此於反應器 55 201222146 内揭月匕夠抑制共聚合反應速度最慢的單體被消耗而相對於 成相對不足的情況’因此即便反應器_單體的存 里=，亦谷易生成接近目標組成的單體組成的聚合物。 ㈣根據本實施形態，可減少自主步驟的開始至後 的:束為止的期間内所生成的聚合物中的單體單元的 ^ 的偏差，故可減小聚合步驟中所生成的聚合物 (Ρ)中的早體單元的含有比率的偏差。 因此’根據本實施形態，可再現性良好地獲得對於 解)性良好且用於抗_組成物時具有高感光度的聚 夕’本實施形態的聚合物亦可應用於抗钮劑用途以 =生可獲得溶解性的提昇效果以外，亦可期待各 〈抗钮劑組成物&gt; 和實施形態的抗蝴組成物是將本實施形態的 衫i程料合物溶解於抗贿射來製備。作為抗 ^，可列舉與聚合物的製造巾所使用的上述聚合溶劑相同 ^本實施形態的抗·組成物為化學增幅型抗_组 =物時，進而含有藉由光化射線或放射線的照射而產生酸 的化合物（以下，稱為光酸產生劑）。 (光酸產生劑） 光酸產生劑可自於化學增幅型抗韻劑組成物中公 “酉久產生劑中任意地選擇。光酸產生劑可單獨使用1種， 56 201222146 HUZOQpif 亦可併用2種以上。 作為光酸產生劑，例如可列舉：鏽鹽化合物、磺醯亞 胺化合物、砜化合物、磺酸酯化合物、二疊氮醌化合物、 重氮曱烷化合物等。 抗蝕劑組成物中的光酸產生劑的含量相對於聚合物 100質量份，較佳為0.1質量份〜2〇質量份，更佳為〇5 質量份〜10質量份。 (含氮化合物） 化學增幅型抗钕劑組成物亦可含有含氮化合物。藉由 含有含氮化合物，抗蝕圖案形狀、曝光後延遲（post Exposure Delay)經時穩定性等進一步提昇。即，抗蝕圖案 的剖面形狀更接近矩形。另外，有時於半導體元件的量產 線等上’對抗蚀膜照射光，繼而進行洪烤（p〇st Εχρ〇_ Bake，ΡΕΒ)後，於接下來_影處理之前_間内須放 置數小時’而由上述放置（經時）所引起的抗㈣案的剖 面形狀的劣化的產生進一步得到抑制。 作為含氮化合物，較佳為胺，更佳為二級低級脂肪族 胺、三級低級脂肪族胺。 抗餘劑組成财的含氮化合物的含量相對於聚合物 100質量份，較佳為0.01質量份〜2質量份。 (有機羧酸、磷的含氧酸或* 1、 化學增幅型抗鋪組成物亦;;^有有機_、鱗的含 氧酸或其衍生物（以下，將該些總稱為酸化合物）。藉由含 有酸化合物，可抑獅含氮化合物的概所引起的感光度 57 201222146 劣化’另外，抗蝕圖案形狀、曝光後延遲經時穩定性等進 一步提昇。 作為有機綾酸’可列舉：丙二酸、檸檬酸、蘋果酸、 丁二酸、笨曱酸 '水楊酸等。 作為磷的含氧酸或其衍生物，可列舉磷酸或其衍生 物、膦酸或其衍生物、次膦酸或其衍生物等。 抗姓劑組成物中的酸化合物的含量相對於聚合物100 質量份’較佳為0.01質量份〜5質量份。 (添加齊ij ) 本實施形態的抗蝕劑組成物視需要亦可含有界面活性 劑:其他抑制劑、敏化劑、防光暈劑、保存穩定劑、消泡 劑等各種添加劑。該添加劑只要是該領域中公知者，則可 使用任何添加劑。另外，該些添加劑的量並無特別限定， 只要適宜決定即可。 &lt;形成有圖案的基板的製造方法&gt; 對本發明的實施形態的形成有圖案的基板的製造方法 的一例進行說明。 首先，於欲形成所期望的微細圖案的矽晶圓等基板的 被加工面上，藉由旋塗等而塗佈本實施形態的抗蝕劑組成 物。然後，藉由烘烤處理（預烤）等對塗佈有該抗蝕劑組 成物的基板進行乾燥，藉此於基板上形成抗賴。For example, by using one type of Lok (U1) having a uniform monomer composition and a monomer content (concentration) as the solution Uc, the drip acceleration can be continuously reduced by &gt;', and the drip acceleration can be gradually reduced. Alternatively, two or more kinds of solutions (Ub U2 Uf) in which the monomer compositions are the same (the above error range is allowed), but the contents (concentrations) of the monomers are different from each other may be used as the solution Uc. In this case, even if the dropping rate is fixed, by sequentially adding two or more kinds of solutions in such a manner that the concentration of the monomer is decreased, the supply of the monomer per unit time can be gradually or stepwisely reduced. More specifically, when the dropwise addition from the start of the solution Uc to the end of the dropwise addition is taken as the post-dropping time, and the total supply amount of the monomer of the latter step is divided by the time obtained as the average supply speed, The period from 0% to k% (k is 5 to 95) is used as a high-speed supply period for the supply of the unit at a speed of (4)^2, and the S speed is higher. In the reactor, the % of the total supply amount of the monomer of the subsequent step is adjusted to % to 95% by mass. The k is preferably 2G% to 8G%, and thus is better for the regulation. The monomer supplied to the reaction correction during the supply period is more preferably a subsequent step / υ 罝〇 / 〇 ~ 85% by mass. In the subsequent step, when the solution Ue_ is added dropwise to the reaction n, a polymerization initiator must be present in the reaction. Therefore, it is preferred to supply a polymerization initiator in the reactor in the subsequent step. The solution Uc may contain a polymerization initiator, or a solution containing a polymerization initiator (polymerization initiator solution) may be added dropwise from the solution Uc. f These are combined. For example, when the polymer (P) in the present embodiment is a lithographic process polymer, the total amount of the monomer supplied to the reactor in the subsequent step (total supply amount of the monomer in the subsequent main step) 100 mol%, poly: the amount of the initiator used (the total amount of the polymerization initiator in the subsequent step) is preferably in the range of 1 mol% to 25 mol%, more preferably 1.5 mol%. ~20% of grass ear%. After the completion of the subsequent step, that is, after the dropwise addition of the solution Uc is completed, a holding step, a step, a purification step, and the like for maintaining the polymerization temperature in the reactor may be appropriately performed as needed. According to the findings of the inventors of the present invention, in the dropwise addition polymerization, when only the monomer solution having the same monomer composition and target composition is continuously added dropwise to the reactor, the polymer formed immediately after the start of 1&amp; The monomer unit has a larger difference between the ratio of the target unit and the target domain, and is gradually closer to the target with the coma, but if it enters the holding step after the completion of the dropwise addition of the monomer solution, The difference between the content ratio of the single element of the raw material and the target composition gradually becomes larger. Specifically, the longer the elapsed time in the holding step, the more significantly the composition ratio of the monomer unit derived from the monomer having the slowest copolymerization rate in the polymer produced from the =. From this, it can be considered that when the dropwise addition of the bulk liquid is completed, the monomer having the highest k-co-polymerization rate in the reactor remains excessively with respect to the target. 54 201222146 -τν/^οομίΐ, 本贝施u' First, in the main step, the monomer content ratio solution Sa and the solution Tb are designed by using the above-mentioned stable state, and the polymerization reaction is started from the beginning. Thereafter, a polymer molecule having a composition substantially the same as the target composition is generated, and the state is continued. Therefore, the poly σ product generated in the main step becomes a decrease in the content ratio of the monomer unit. In addition, 'after the main step' is set to not carry out the holding step, and the ratio of the direct φ: the slowest monomer of the co-polymerization reaction rate is less than the post-gamma of the solution UC of the target composition, and the ratio is more than the target composition. The monomer in which the copolymerization reaction rate is the slowest is supplied to the reactor. It is preferred that the solution Uc does not contain the monomer having the slowest copolymerization rate, and only the monomer other than the monomer having the slowest copolymerization reaction rate is supplied in the subsequent step. In this way, in the reactor at the end of the dropwise addition of the solution Tb, the polymer having the most excellent copolymerization reaction rate remaining excessively with respect to the target composition is efficiently consumed, thereby generating a polymer, thereby preventing the main step. The difference between the content ratio of the monomer unit in the produced polymer and the target composition becomes larger at 10 minutes. Therefore, the deviation of the content ratio of the monomer unit in the finally obtained polymer (p) can be reduced. In addition, by setting the monomer composition of the solution Uc to the composition u,c ' obtained by the design method using the above factors, the content ratio of the monomer unit in the polymer produced after the main step can be made closer to the target composition. . In the subsequent step, the supply amount per unit time of the unit supplied by the dropwise addition of the solution Uc (preferably, the monomer other than the monomer having the slowest copolymerization reaction rate) is The passage of time is reduced, whereby the monomer which is the slowest in suppressing the copolymerization reaction is consumed in the reactor 55 201222146, and is relatively inferior to the case of being relatively insufficient. Therefore, even if the reactor_monomer remains, It is also easy to generate a polymer composed of monomers close to the target composition. (4) According to the present embodiment, it is possible to reduce the variation of the monomer unit in the polymer formed during the period from the start of the autonomous step to the time after the bunching, so that the polymer formed in the polymerization step can be reduced. The deviation of the content ratio of the early body unit in ). Therefore, according to the present embodiment, the polymer having good reproducibility and good sensitivity for the anti-composition can be obtained, and the polymer of the present embodiment can also be applied to the anti-button agent application. In addition to the effect of improving the solubility, it is also expected that each of the "anti-button composition" and the anti-butter composition of the embodiment are prepared by dissolving the lacquer composition of the present embodiment in a resisting brittle. The anti-cab composition of the present embodiment is the same as the above-mentioned polymerization solvent used in the production of the polymer. When the anti-composition material of the present embodiment is a chemically amplified anti-group=substance, it further contains irradiation with actinic rays or radiation. An acid generating compound (hereinafter referred to as a photoacid generator). (Photoacid generator) The photoacid generator can be arbitrarily selected from the chemical growth-increasing agent composition. The photoacid generator can be used alone. 56 201222146 HUZOQpif can also be used in combination. The photoacid generator may, for example, be a rust salt compound, a sulfonium imide compound, a sulfone compound, a sulfonate compound, a diazide compound or a diazane compound. The content of the photoacid generator is preferably 0.1 parts by mass to 2 parts by mass, more preferably 5% by mass to 10 parts by mass, based on 100 parts by mass of the polymer. (Nitrogen-containing compound) Chemically amplified anti-caries agent composition The material may further contain a nitrogen-containing compound, and the shape of the resist pattern, post-exposure delay, stability over time, etc. are further improved by containing a nitrogen-containing compound, that is, the cross-sectional shape of the resist pattern is closer to a rectangle. Sometimes, the resist film is irradiated with light on a mass production line or the like of a semiconductor element, and then subjected to flooding (p〇st Εχρ〇_ Bake, ΡΕΒ), and then placed for several hours before the next _ shadow processing Further, the occurrence of deterioration of the cross-sectional shape of the anti-(4) case caused by the above-mentioned placement (time-lapse) is further suppressed. As the nitrogen-containing compound, an amine is preferred, and a second-order lower aliphatic amine, a tertiary lower aliphatic group is preferred. The content of the nitrogen-containing compound of the anti-reagent composition is preferably 0.01 parts by mass to 2 parts by mass based on 100 parts by mass of the polymer. (Organic carboxylic acid, phosphorus oxyacid or *1, chemical amplification type resistance The composition of the pavement is also;;; an organic acid, an oxo acid of a scale or a derivative thereof (hereinafter, collectively referred to as an acid compound). By containing an acid compound, the sensitization caused by the ash-containing nitrogen compound can be obtained. Degree 57 201222146 Deterioration 'In addition, the shape of the resist pattern, the delay after exposure, and the like are further improved. As the organic tannic acid, there may be mentioned: malonic acid, citric acid, malic acid, succinic acid, and succinic acid' water. Salicylic acid, etc. Examples of the oxyacid of phosphorus or a derivative thereof include phosphoric acid or a derivative thereof, a phosphonic acid or a derivative thereof, a phosphinic acid or a derivative thereof, and the like. Relative to polymer 100 mass It is preferably 0.01 parts by mass to 5 parts by mass. (Addition of ij) The resist composition of the present embodiment may optionally contain a surfactant: other inhibitors, sensitizers, antihalation agents, and storage stability. Any additives such as a solvent and an antifoaming agent may be used as long as they are well known in the art. The amount of the additives is not particularly limited, and may be appropriately determined. (Manufacturing method) An example of a method for producing a patterned substrate according to an embodiment of the present invention will be described. First, spin coating is performed on a surface of a substrate such as a germanium wafer on which a desired fine pattern is to be formed. The resist composition of this embodiment is applied, for example. Then, the substrate coated with the resist composition is dried by baking treatment (pre-baking) or the like to form a resist on the substrate.

、繼而，經由光罩對抗蝕臈進行曝光而形成潛像。作為 曝光用光’較佳為25〇 nm以下的波長的光。例如較佳為 KrF準分子雷射、ArF準分子雷射、F2準分子雷射、EUV 201222146 4UZ««pif 分子雷射。另外，亦可照射電子束。 裝置===曝光，’以在該抗賴與曝光 氣三燒基胺等高折射輪體的狀態全 使’適宜進行熱處理（曝光魏烤，peb)，然後 中顯影_觸’並使曝光部分溶解於顯影液 性顯影液。 秘i貞减，可列舉公知的驗 =彡後’利簡料對基㈣輯行淋洗處理。如此， 於基板上形成抗蝕圖案。 來成有抗侧案的基板適宜進行熱處理（後烘烤） 來強化抗侧，並選擇性地_無抗_的部分。 餘刻後’湘獅娜抗㈣絲，藉此獲得形 从細圖案的基板。 尤其，藉由微影製程用聚合物的製造方法的實施形態 、）所獲知的微影製程用聚合物對於溶劑的溶解性優 異，並且可形成高感光度的抗蝕膜。 人因此，可谷易且良好地進行製備抗钱劑組成物時的聚 &amp;物對於抗蝕溶劑的溶解。另外，抗蝕劑組成物可獲得對 ^鹼性顯影液的優異的溶解性，有助於感光度的提昇。另 外，因抗蝕劑組成物中的不溶物少，故於形成圖案時，不 易產生起因於該不溶物的缺陷。 因此，藉由使用該抗蝕劑組成物製造形成有圖案的基 板，可於基板上穩定地形成缺陷少且高精度的微細的抗蝕 59 201222146 可較佳地用於借助如下的微影製程實現的Then, the resist is exposed through the photomask to form a latent image. The light for exposure ' is preferably light having a wavelength of 25 Å or less. For example, KrF excimer laser, ArF excimer laser, F2 excimer laser, EUV 201222146 4UZ ««pif molecular laser are preferred. In addition, an electron beam can also be irradiated. Device ===exposure, 'in the state of the high-refraction wheel body such as the anti-glare and the exposure gas tricarbylamine, the heat treatment is appropriate (exposure of the fire, peb), then the development of the touch-and-exposure portion Dissolved in a developer developing solution. The secret is reduced, and the well-known test can be listed. Thus, a resist pattern is formed on the substrate. The substrate to be formed into an anti-side case is suitably subjected to heat treatment (post-baking) to strengthen the anti-side, and selectively _ no anti-- portion. After the engraving, 'Xiang Shi Na anti-(four) silk, thereby obtaining a substrate shaped from a fine pattern. In particular, the lithographic process polymer obtained by the embodiment of the method for producing a lithography process is excellent in solubility in a solvent, and a high-sensitivity resist film can be formed. Therefore, the dissolution of the poly- &amp; substance in the anti-money agent composition at the time of preparation of the anti-money composition can be carried out well. Further, the resist composition can obtain excellent solubility to an alkaline developing solution and contribute to an improvement in sensitivity. Further, since the insoluble matter in the resist composition is small, defects due to the insoluble matter are less likely to occur when the pattern is formed. Therefore, by using the resist composition to fabricate the patterned substrate, it is possible to stably form a fine resist 59 with low defects and high precision on the substrate. 201222146 can be preferably used for the following lithography process. of

Is蚊要求使用高感光度及高解析度的 二二雪2利用波長250 nm以下的曝光用光的光微 :影製程’例如是使用ArF準分子雷射 (193 nm)的微影製程。 再者，當製造利用波長MO nm以下的 微所使用的抗蝕劑組成物時，較佳為以使聚合物 於“曝光用光的波長巾為透明的方式來適宜選擇單體。 2聚i物的評價方法（三單元組的分率的預測）&gt; 物的二二=式’對本發明的實施形態的評價共聚合 物方法進行說明。圖丨是表示_該一實 施=的共聚合物觸方法進行轉合物鱗價的共聚合 物评價裝置的構成例的概略方塊圖。 :聚合物評價裝置包括:目標變數分析部1卜 波形處理部U、說明變數分析部13、 品分析部15、儲存部16、顯示部17及控制部成二 比1 = =P11根據各單體單元的共聚合反應性 ’异出並輸出作為已知樣品的共聚合 的三單元組的分率。 ）分w早涖早兀 波形處理部12進行NMR^， 合物·_由感應衰临ee她⑽ 信號的傅里葉變換及資料處理。 f明分析部13根據已知樣品及未 測定中的對於化學位移的信號強“輸出說明變數 201222146 HUZOOpif (Partial Least 歸，模型的回歸式)，生成:t模上型== 歸式及回歸模型的係數）。 听棋玄·的口 樣品分析部15使用回歸模型，根擄未 移與信號強度，算出未知樣品的各個單元;^ : 的比例，即三單元組分率的預測值。 Μ-早兀、、且Is mosquito requires the use of high-sensitivity and high-resolution Er 2 snow 2 to utilize light exposure light with wavelengths below 250 nm. The shadow process is, for example, a lithography process using an ArF excimer laser (193 nm). Further, when a resist composition used for micro-doses having a wavelength of MO nm or less is produced, it is preferable to appropriately select a monomer so that the wavelength of the wavelength of the exposure light is transparent. Method for evaluating a substance (predicting the fraction of a triad) &gt; "Two-two formula of the substance" The method for evaluating the copolymer of the embodiment of the present invention will be described. Fig. 丨 shows a copolymer of the same embodiment = A schematic block diagram of a configuration example of a copolymerization evaluation apparatus for performing a conversion valence. The polymer evaluation apparatus includes a target variable analysis unit 1 waveform processing unit U, a description variable analysis unit 13, and a product analysis unit. 15. The storage unit 16, the display unit 17, and the control unit are in a ratio of 1 to =P11, and the fraction of the copolymerized triad which is a known sample is outputted according to the copolymerization reactivity of each monomer unit. The W-ray analysis unit 12 performs the Fourier transform and the data processing of the IF (10) signal by the induction fading. The f analysis unit 13 is based on the known sample and the unmeasured Strong signal of chemical shift "Output Description Variable 2012 22146 HUZOOpif (Partial Least, regression of the model), generated: t-module == coefficient of the normalized and regression model). The mouth analysis unit 15 uses the regression model to calculate the ratio of the unit of the unknown sample, i.e., the predicted value of the three-unit component rate, using the regression model. Μ-早兀,, and

，存部16儲存說明變數、樣品模型及三單元心 的計异過程及評價結果等資料。 、 控制18將上述各部的計算過程及作為呷價社果的 表示三單元組的比例的三單元組分率等製= 表，並顯示於顯示部17中 表成谩述的、，.。果 制命18對自未圖示的鍵盤所輸入的資料及控 者將ί未圖:二對共聚合物評價褒置内的各部輸出，或 =自未I的NMR裝置所輸人的㈣向波形處理部η —丨用太: '圖卜對該圖1的共聚合物評價裝置所進 ==態+的共聚合物評價方法的共聚合物的 下所==二⑴，目標變數分析部11如以 一 Γϋΐ分析部11藉由計算而求出共聚合物中的三 :二二“ ’即三單元組分率。此處，所謂三單元組， 疋曰Λ σ 所含有的連續地鍵結的3個構成單元。另 61 201222146 外’所謂各個單體單元的三單元組，是指3個同一麵的 單體單元連續地鍵結而成的結構。於包含11個構成單元的 共聚合物中，各個單體單元的三單元組存在n種。 3個構成單元的鏈例如於將構成單元設為A與B這2 種（n-2)的情況下’作為組合，存在AAA、AAB、Bab、 ^ΒΛ、BBA、BBB這6種。該6種之中，各個單體單元的 三單元組（僅包含單體的三單元組）存在八八八、；636這2 種。可根據下述計算式（H)求出各個單體單元的三單元 組的分率（％)。 _ [數3] P{j j j) (%) =1 ΟΟχ [Μ1 ,] ΧΡ,;χρ.( ,、 ρ [MJ] . ·.⑻ i,z= 上述式中’ [M’j]是共聚合物中的單體單元』的莫耳分 率，於單體（單元）j為共聚合物的成長末端的構成單元 鲁 時’ Pjj疋與單體（單元）j進行反應的概率，[%]、[Mh] 是反應系統中的各單體（單元）j、h的莫耳分率，是自 單體（單元）j至單體（單元）h的共聚合反應性比' 藉由上述計算式（Η)所求出的各個單體單元的三單 元組分率於共聚合物的生成依照一階馬可夫（first 〇rder Markov)統計時，可根據使用共聚合反應性比、及將聚合 率抑制為10%以内的共聚合物的組成的計算而求出。 62 201222146 wzoopif ㈣二Ϊ㈣分析部11使單體單元的料分率的組合、斑 單元的莫耳分率的組合_上述計算式⑻、 3製成莫耳分率.三單元組分率表，且將其寫入並= 儲存部16中。The storage unit 16 stores information such as the variables, the sample model, and the calculation process of the three-unit heart and the evaluation results. The control unit 18 calculates the calculation process of each of the above-mentioned parts and the three-element component ratio of the ratio of the three-unit group, which is shown in the display unit 17, and is displayed on the display unit 17, and is described in detail. The data and the controller input from the keyboard (not shown) will not be shown: the output of each part in the two pairs of copolymer evaluation devices, or the (four) direction of the input from the NMR device without I The waveform processing unit η - 丨 : ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共11 Calculate the three: two-two "', ie, the three-unit component ratio in the copolymer by calculation by the analysis unit 11. Here, the so-called three-unit group, the continuous bond contained in 疋曰Λσ Three constituent units of the junction. Another 61 201222146 The 'three-unit group of each monomer unit refers to a structure in which three monomer units of the same plane are continuously bonded. The copolymerization of 11 constituent units is included. In the case of the three-unit group of each monomer unit, there are n kinds. The chain of the three constituent units is, for example, when the constituent unit is two types (n-2) of A and B. 6 kinds of Bab, ^B, BBA, BBB. Among the 6 kinds, the triad of each monomer unit (only contains monomeric There are two types of unit groups: 888 and 636. The fraction (%) of the triad of each monomer unit can be obtained according to the following formula (H). _ [Number 3] P{jjj) ( %) =1 ΟΟχ [Μ1 ,] ΧΡ,;χρ.( ,, ρ [MJ] . ·.(8) i,z= In the above formula, '[M'j] is a monomer unit in the copolymer] Ear fraction, the probability that the monomer (unit) j is the constituent unit of the growth end of the copolymer, Luh 'Pjj疋 reacts with the monomer (unit) j, [%], [Mh] is the reaction system The molar fraction of each of the monomers (units) j and h is a copolymerization reactivity ratio from the monomer (unit) j to the monomer (unit) h, which is determined by the above calculation formula (Η) The triad fraction rate of the monomer unit is based on the first-order Markov (first 〇rder Markov), and can be based on the copolymerization reactivity ratio and the copolymerization rate of 10% or less. 62 201222146 wzoopif (4) Dimensional (4) Analysis unit 11 combines the fractions of the monomer units and the moiré ratio of the spot units. The above calculation formulas (8) and 3 Mole fraction. Triad fraction table, and writes it in the storage unit 16 and =.

^繼而，波形處理部12進行藉由NMR測定所獲得的共 來合物或聚合物的FID (Free Indueti〇n D啊）信號的 里葉變換及資料處理。 即，波形處理部11進行藉由NMR測定所獲得的fid 信號的傅里葉·，生成具杨學位移（辦成分）及信 號強度（NMR光譜的光譜強度）的資訊的NMR光譜信號。 此時，對應於所測定的觀測核的種類，設定BF ( Br〇adening Factor ’擴張因數）（事先於實驗中進行測定，然後設定對 應於各個觀測核的擴張因數），藉此可提昇所對應的觀測核 的光譜解析度，因此可提昇共聚合物、聚合物中的包含單 體的鏈資訊的組成的推斷精度。 另外’用於NMR測定的裝置只要使用市售品即可， 並無特別限定’但就化學位移的解析度高的觀點而言，較 佳為使用磁場強度為7特士拉（tesia)(作為咕核的頻率 為300 MHz)以上的NMR裝置。 NMR測定中的觀測核只要對應於共聚合物（p)的種 類而適宜選擇即可，但就相對同位素豐度或感光度高的觀 點而言，較佳為1Η、13C、19F、29Si 〇 用於NMR測定的樣品管的直徑只要對應於共聚合物 63 201222146Then, the waveform processing unit 12 performs a Fourier transform and data processing of the FID (Free Indueti〇n D) signal of the copolymer or polymer obtained by NMR measurement. In other words, the waveform processing unit 11 performs Fourier· of the fid signal obtained by NMR measurement to generate an NMR spectrum signal having information on the Young's shift (component) and the signal intensity (spectral intensity of the NMR spectrum). At this time, BF (Br〇adening Factor 'expansion factor) is set corresponding to the type of the observed nuclear nucleus (measured in advance in the experiment, and then the expansion factor corresponding to each observation nucleus is set), thereby improving the correspondence By observing the spectral resolution of the core, it is possible to improve the estimation accuracy of the composition of the chain information including the monomer in the copolymer or the polymer. In addition, the apparatus used for the NMR measurement is not particularly limited as long as it is a commercially available product. However, from the viewpoint of high chemical shift resolution, it is preferable to use a magnetic field strength of 7 tesia (as The NMR device with a frequency of nucleus of 300 MHz or more. The observation nucleus in the NMR measurement may be appropriately selected as long as it corresponds to the type of the copolymer (p), but is preferably used for 1 Η, 13 C, 19 F, 29 Si from the viewpoint of high isotopic abundance or sensitivity. The diameter of the sample tube determined by NMR is as long as it corresponds to the copolymer 63 201222146

_ 上〆易A (p)的種類而適宜選擇即可，當選擇1H、作為觀測核 時，就相對同位素豐度高的觀點而言，較佳為3 mm(p = 上，更佳為5 mm(p以上。另外，當選擇nc、29Si作為觀 測核時’就可獲得靈敏度更高的信號強度的觀點而言，較 佳為5 mmq)以上’更佳為1〇 mmcp以上。 用於NMR測定的共聚合物及聚合物的試樣濃度並無 特別限定，但就可獲得靈敏度更高的信號強度的觀點而 言，較佳為1質量％以上，另外，更佳為5質量％以上， 進而更佳為1〇質量％以上。 鲁 另外’就抑制因試樣溶液的黏度造成的緩和時間的影 響的觀點而言，較佳為5〇質量％以下，更佳為3〇質量％ 以下’進而更佳為20質量％以下。 用於NMR測定的氘化溶劑只要可使共聚合物及聚合 物溶解，則並無特別限定，例如可列舉：氘化氣仿 (CDCI3)、氘化二甲基亞砜（DMS〇_d6)、氧化氘 氘化曱醇（ch3od或cd3od)、氘化四氫呋喃（C4D4〇)、 氘化六氟異丙醇（HFIP-d2)等。另外，亦可添加四甲基矽 φ 烷（Tetramethylsilane，TMS)或CFCI3作為化學位移的某 準物質。 1 NMR測定時的試樣溫度只要是試樣溶劑的沸點以 下、或者不產生共聚合物及聚合物的分解或變質的溫度， 則並無特別限定’但就可獲得靈敏度更高的信號強=觀 點而言，較佳為儘可能為高溫。 NMR測定時的資料累計次數並無特別限定，只要對應 64 201222146 測核的種類而適宜選擇即可’當選擇1h、19f 4次以：’就相對同位素豐度高的觀點而言，較佳為 ，更佳為Μ次以上。另外，當選擇1¾、29Si作 ί觀’就可獲得靈敏度更高的信號強度的觀點而 二^ \15GG次以上，更佳為_次以上。此處，所 次的信號’是指多次獲取職信號’使該多 為將該經重4的信號作 13如UlT$說明變數分析過程（Π)’說明變數分析部 以下所讀生成錢品的鱗⑽及信號強度。 勺人^變數分析部13進行經傅里葉變換的化學位移與 NMR光譜信號的相位對準（使各個NMR光 2=基線與頻_平㈣方式進行校正4值 ϋ、ίΓ先奴的積分翻（將後述的化學位移的範圍 圍）内的強度面積)及成為基準的化學位_ The type of Shangyuyi A (p) is suitable for selection. When 1H is selected as the observation nucleus, it is preferably 3 mm from the viewpoint of high isotope abundance (p = upper, more preferably 5). Mm (p or more. In addition, when nc, 29Si is selected as the observation nucleus, from the viewpoint of obtaining a signal intensity with higher sensitivity, it is preferably 5 mmq or more), more preferably 1 〇 mmcp or more. The concentration of the sample of the measured copolymer and the polymer is not particularly limited, but is preferably 1% by mass or more, and more preferably 5% by mass or more, from the viewpoint of obtaining a signal intensity with higher sensitivity. Furthermore, it is more preferably 1% by mass or more. From the viewpoint of suppressing the influence of the relaxation time due to the viscosity of the sample solution, it is preferably 5% by mass or less, more preferably 3% by mass or less. Further, it is more preferably 20% by mass or less. The deuterated solvent used for the NMR measurement is not particularly limited as long as it can dissolve the copolymer and the polymer, and examples thereof include deuterated gas (CDCI3) and deuterated dimethyl ether. Sulfone (DMS〇_d6), oxidized decyl sterol (ch3od or cd3od) Deuterated tetrahydrofuran (C4D4〇), deuterated hexafluoroisopropanol (HFIP-d2), etc. Alternatively, Tetramethylsilane (TMS) or CFCI3 may be added as a quasi-substance for chemical shift. 1 NMR The sample temperature at the time of measurement is not particularly limited as long as it is at or below the boiling point of the sample solvent or does not cause decomposition or deterioration of the copolymer and the polymer, but a signal strength with higher sensitivity can be obtained. It is preferable that the temperature is as high as possible. The cumulative number of data in the NMR measurement is not particularly limited, as long as it is appropriately selected according to the type of 64 201222146 nuclear test, 'when 1h and 19f are selected 4 times: 'is relatively isotopic From the viewpoint of high degree, it is preferably more preferably more than one time. In addition, when selecting 13⁄4, 29Si for ' view, the viewpoint of higher sensitivity signal strength can be obtained, and more than ^15 GG times or more, more preferably It is _ times or more. Here, the secondary signal 'refers to the acquisition of the job signal multiple times', so that the signal of the weight 4 is 13, such as UlT$, the variable analysis process (Π)', the description of the variable analysis section The scale of the money that is generated And the signal intensity. The scooping person/variable analysis unit 13 performs phase alignment of the Fourier-transformed chemical shift and the NMR spectral signal (correction of each NMR light 2=baseline and frequency_flat (four) method) The integral of the slave (intensity area within the range of the chemical shift described later) and the chemical position as the reference

Nivm ^準化），並輸出包含化學位移與信號強度的 光;w信號的定量使用資訊g (後述的矩陣）。此處， =予位移的㈣使用包含構成共聚合物的各個構元的 觀測核的範圍。 —即’於NMR光ϋ的分割與積分中，關鍵在於進行傅 里葉變換後的化學位移的光譜（信號強度）的積分的分割 的間隔。 即說明變數分析部13針對m種共聚合物或混合聚 65 201222146Nivm ^ normalization), and output light containing chemical shift and signal intensity; quantitative information of w signal using information g (matrix described later). Here, (4) of the pre-displacement uses a range of observation nuclei containing the respective constituents constituting the copolymer. That is, in the division and integration of the NMR pupil, the key is the division interval of the integral of the spectrum (signal intensity) of the chemical shift after the Fourier transform. That is, the variable analysis unit 13 is described for m kinds of copolymers or mixed poly 65 201222146

合物的樣品中的第M 的間隔將化學位移p 為1〜m的整數）’以固定 割的樣品中的第(p為整數）地分割，並將經分 w弟g個的積分值 另外，說明變叙八t kg 合計刀析部13將經分割的光譜的積分值的 十;^議，而進行標準化的處理。 fki + fk2+...fkg+... + fkp=1〇〇The interval of the Mth in the sample of the compound is such that the chemical shift p is an integer of 1 to m), and the (p is an integer) of the fixed cut sample is divided, and the integral value of the divided g is added. The description will be given to the normalization process in which the knives of the divided octaves are divided into three. Fki + fk2+...fkg+... + fkp=1〇〇

Lg-ave 的4:，根據下式求出所有 m種樣品的第g個的積分值 fgf (flg+f2g+...fkg+... + fmg)/m 後，經p等分的所有分割光譜求出平均值 範圍而椤準 樣品的積分值，使藉由NMR光譜的頻率 分割範^ ^、化的光譜的每個積分減去相對應的化學位移的 變成下气、、句值fg-ave ’求出基準化的積分值bkg。即， b g-ave '、結果’第k個樣品的光譜強度由下式的向量表示 66 201222146 xk= (bkl、bk2、...、bkg、…、bkp) 而且，說明變數分析部13若彙集關於所有m種樣品 的光譜強度，則生成定量使用資訊〇作為由以下的（ii)D 式所示的矩陣。該定量使用資訊G成為變成生成說明變數 的基礎的化學位移及信號強度（積分後）。 [數4] — -η …kp G = : ... ： . · * (11) Λ^ι…心 另外，說明變數分析部u對各樣品附加固有的 ，資訊’並使該樣品識別資訊與該樣品識別資訊所示:樣Lg-ave 4:, after dividing the integral value fgf (flg+f2g+...fkg+... + fmg)/m of the gth of all m samples according to the following formula, all the divided spectra by p-division The average value range is obtained and the integral value of the sample is obtained, so that the frequency division of the NMR spectrum is reduced, and the corresponding chemical shift is subtracted from the corresponding chemical shift to become the lower gas, and the sentence value fg-ave 'Get the integrated integral value bkg. That is, b g-ave ', the result 'the spectral intensity of the kth sample is represented by a vector of the following formula 66 201222146 xk= (bkl, bk2, ..., bkg, ..., bkp) Further, the variable analysis unit 13 will be described. When the spectral intensities of all the m samples are collected, a quantitative use information is generated as a matrix represented by the following formula (ii)D. The quantitative use information G becomes a chemical shift and a signal intensity (after integration) which are the basis for generating the explanatory variables. [Number 4] — η ...kp G = : ... : . · * (11) Λ^ι... In addition, the variable analysis unit u adds a unique information to each sample, and makes the sample identification information and The sample identification information shows:

=的化學娜及信㈣度相關聯，製祕 = 存於儲存部16中。 取兀馬入、儲 丨六王土取邯14如以 下所示般生成說明變量側的模型。 型的= 將說明變量側的模型式即回歸模 為說明變量側分數， 。此處，所謂負荷， p為說明變量 是指可獲取最 G = TP + Rg ，而設定於内部。 於該模型式中，τ 側負荷’ RG為殘潰矩陣 67 201222146 ^tu^-oopii 多的因子（樣品的數值）的分散的軸的方向座標态乙。 於模型生成部14中，將目標變量側的模型式即回歸模 型回歸式的定義設為： C = UQ + Rc ，而設定於内部。 該式中，C為各單體單元的三單元組分率（預測值） 的數值資料，且為由下述（12)式所表示的矩陣，於該矩 陣中，Cl...cn是表示各單體單元的三單元組分率的數值的 向量。 [數5] C = [ci C2 ·· cn] 1 (12) 另外，U為目標變量側分數，Q為目標變量側負荷， Rc為殘渣矩陣。 而且，模型生成部14根據各單體單元的三單元組分率 已知的已知樣品的NMR測定的結果，經由第1加權向量 Wl，如下述式般定義該NMR測定結果的NMR光譜的矩陣 G、及彙集了各已知樣品的第一單體單元的三單元組分率 的向量q。 G= CjWi + R... ( i) 自上述（i)式中排除殘渣矩陣R，並自左側乘以q 68 201222146 4UZ88pif V或反矩陣WO .1，根據以下的式算出第 1加榷向$Wl的妥協解。 囬第W1= (ciTCl) -Vg... (ii) 旦Ί’模型生成部14根據丽尺光譜G與第1加權θ 1Wl，使用以下的式求出第1說明變量侧分數tl。= chemical na and letter (four) degree associated, secret recipe = stored in the storage unit 16. Take the 兀马入,储储六王土取邯14 to generate the model on the variable side as shown below. The type = will describe the model on the variable side, ie the regression model, to illustrate the variable side score, . Here, the load, p is the explanatory variable, which means that the most G = TP + Rg can be obtained and set internally. In the model, the τ side load 'RG' is the residual matrix 67 201222146 ^tu^-oopii The multi-factor (sample value) of the scattered axis direction coordinate state B. In the model generation unit 14, the model expression of the target variable side, that is, the regression model regression equation, is defined as C = UQ + Rc and is set internally. In the formula, C is a numerical data of a triad fraction (predicted value) of each monomer unit, and is a matrix represented by the following formula (12), in which Cl...cn is a representation A vector of values for the triad fraction of each monomer unit. [Equation 5] C = [ci C2 ··cn] 1 (12) In addition, U is the target variable side score, Q is the target variable side load, and Rc is the residue matrix. Further, the model generating unit 14 defines a matrix of the NMR spectrum of the NMR measurement result by the first weighting vector W1 based on the result of the NMR measurement of the known sample in which the triad fraction of each monomer unit is known. G, and a vector q summarizing the triad component ratios of the first monomer units of each known sample. G = CjWi + R... (i) The residue matrix R is excluded from the above formula (i), and multiplied by q 68 201222146 4UZ88pif V or inverse matrix WO .1 from the left side, and the first twist direction is calculated according to the following formula $Wl's compromise solution. (1) The model generation unit 14 obtains the first explanatory variable side score t1 from the scale spectrum G and the first weight θ 1W1 using the following equation.

Gw/ (wlWlT) '1/2=tl..Gw/ (wlWlT) '1/2=tl..

Ill (iIll (i

IV 自该式中排除（消去）殘渣矩陣化，並自左 试明變量側分數tl的轉置矩陣tlT及反矩陣（t ]， =藉由下述式，而如下述式所示般求出第丨目量負 何qi的妥協解。 文里側負 ^ (Λ) Λ】IV. The matrix of the residue is eliminated (eliminated) from the equation, and the transposed matrix tlT and the inverse matrix (t) of the variable side fraction of the variable side are corrected from the left, and are obtained by the following equation. The first item is negatively compromised by the qi. The text is negative ^ (Λ) Λ

Cj... 然後，模型生成部Μ使用C = UQ + Rc的定義式，0 由第1目標變量側分數…，以下述式求出組成向量二與= 69 201222146 H-uzoopif 1目標變量側負荷qi的關係。Cj... Then, the model generation unit uses the definition of C = UQ + Rc, 0 from the first target variable side score..., and finds the composition vector two and = 69 201222146 H-uzoopif 1 target variable side load The relationship of qi.

Ci = uiqi + RM... (vi) 模型生成部14排除（消去）殘渣矩陣反，，，自右侧乘 以第1目標變量側負荷〜的轉置矩陣 &lt;及反矩陣（⑽ιΤ) ’以下述m第1目標變量側分數〜的妥協解。Ci = uiqi + RM... (vi) The model generation unit 14 excludes (eliminates) the residue matrix inverse, and multiplies the transpose matrix &lt; and the inverse matrix ((10) ιΤ) of the first target variable side load from the right side. The compromise solution of the score of the first target variable side of the following m.

Ui = ciqiT (qiqiT) (vii) 然後，經由内部相關係數Si，如下述式般求出第i目 標變量側分數u!與第1說明變量側分數心。 ui = siti... (viii) 另一方面，，當無法藉由此處所得的屮獲得充分的 關聯時，將4代入（i)式的Cl，再次計算（i)〜 的各式，重複該操作直至Ul收斂成固定值為止。此時，模 型生成部14於重複計算之後的Ui成為重複計算之前的七 的0·99〜1.01倍的範圍時，視為Ui已收斂而結束計算。 若求出已收斂的u! ’則分別求出Sl、tl、化、Wi。 然後，模型生成部14根據G==TP + Rg的定義式求出 + ’自該式中排除〇肖去）殘渣矩陣R，，，，並自 左側乘以t!的轉置矩陣及反矩陣（tlTti) -1，而如以下 201222146 ^288pif 的式般求出Pi的妥協解。 Ρι= (Λ) -Vg…（ix) 繼而，使用由上述各式所求出的Ul、屮、Si、&amp;、A， 以下述式表示相當於模型式的殘渣矩陣Rg與殘渣矩陣Rc 的矩陣G2與矩陣c2， 一^2=0^^!... (χ) 第二單體==:= 下述式般求出矩陣G2 02= C2W2 + R2... ( i' 以下，以與（ii)式〜（ix) S2、t2、q2、w2、ρ2。 以下，模型生成部14以相 sn、t3〜tn、q3〜qn、w3〜Wn、P3〜p 方式未出 w〜un、s3. 式相同的方式’求出 u2 71 201222146 H-UXOOpiiUi = ciqiT (qiqiT) (vii) Then, the i-th target variable side score u! and the first explanatory variable side score center are obtained by the internal correlation coefficient Si as follows. Ui = siti... (viii) On the other hand, when it is not possible to obtain sufficient correlation by the 所得 obtained here, 4 is substituted into Cl of (i), and the equations of (i)~ are again calculated and repeated. This operation until U1 converges to a fixed value. At this time, when the Ui after the repeated calculation is in the range of 0·99 to 1.01 times the seven before the repeated calculation, the model generating unit 14 considers that Ui has converged and ends the calculation. When the converged u!' is obtained, Sl, tl, crystallization, and Wi are obtained. Then, the model generation unit 14 obtains the residue matrix R, from the definition of G==TP + Rg, and subtracts the reversal matrix and the inverse matrix from the left side by t! (tlTti) -1, and the compromise solution of Pi is obtained as in the following 201222146 ^288pif. Ρι= (Λ) -Vg (1) Then, using U1, 屮, Si, &amp; A, which are obtained by the above equations, the residue matrix Rg and the residue matrix Rc corresponding to the model formula are expressed by the following formula The matrix G2 and the matrix c2, a ^2=0^^!... (χ) The second cell ==:= The matrix G2 is determined as follows: 02= C2W2 + R2... (i' And (ii) to (2) S2, t2, q2, w2, and ρ2. Hereinafter, the model generation unit 14 does not generate w~un by the phases sn, t3 to tn, q3 to qn, w3 to Wn, and P3 to p. , s3. The same way as 'find u2 71 201222146 H-UXOOpii

Gn —G-tj^Pn 小（χϋ)Gn —G-tj^Pn Small (χϋ)

Cn = C-un.iqn,1==c. 第ηϊ:,·模型Ϊ成部14 “⑴式為基礎’使用彙集了 如下if:私=二單元組分率的向量Cn與第n加權向量…&quot;， 下述式般求出矩陣〇η。Cn = C-un.iqn,1==c. ηϊ:,·Model composition unit 14 “(1) is based on the use of the following if: private = two-unit fraction rate vector Cn and n-th weight vector ...&quot;, The matrix 〇η is obtained by the following equation.

Gn=CnWn + Rn... (j..) 以下 的作兔样，、型生成部14將如上述般求出的每個已知樣品 量”（回歸模型的係數，即回歸式的係數的向 tn、向〜向量Un、向量S1〜向量〜、向量h〜向量 P竹\里^〜向量qn、向量Wl〜向量Wn、向量Pl〜向量 已知樣品的樣品資料而寫入至儲存部16中，並將該 二乍為已知樣品的樣品資料加以儲存。 繼而，作為樣品分析過程（IV)，樣品分析部 15如以 知样不般L基於模型生成部14所生成的樣品資料，算出未 °粟品的三單元組分率（三單元組分率預測值）。 波形處理部12進行藉由NMR#』定所獲得的共聚合物 5聚合物的FID信號的傅里葉變換及#料處理。該波形處 72 201222146 4UZ05pif 理部12的處理與已在已知樣品中說明的處理同樣地，生成 未知樣品的NMR光譜信號。 繼而，與說明變數分析部13所進行的NMR光譜信號 的信號處理同樣地’樣品分析部15進行經傅里葉變換的化 學位移與包含其波形的NMR光譜信號的相位對準、基線 處理、峰值積分及成為基準的化學位移值（標準化）的設 定。此處，化學位移的範圍使用包含構成共聚合物的各個 構成單元的觀測核的範圍。 然，’樣品分析部15將包含化學位移與信號強度的 ^矩陳號的定量使㈣訊A作為下述⑼式所示 = 定量使用資訊八是未知樣品為3(m=3) ::二吏:資訊’但不論未知試樣為1個或多個，均進 [數6] n6¾¾ !_ 1 liGn=CnWn + Rn (j..) The following rabbit-like type, the type generating unit 14 sets each known sample amount as described above (the coefficient of the regression model, that is, the coefficient of the regression equation) The sample data of the known sample is written to the storage unit 16 to tn, vector to vector Un, vector S1 to vector ～, vector h to vector P, 里 ^ 〜 vector qn, vector W1 to vector Wn, vector P1 to vector. In the case of the sample analysis process (IV), the sample analysis unit 15 calculates the sample data generated by the model generation unit 14 based on the sample analysis unit 14 as a sample analysis process (IV). The triad component ratio (predicted value of the triad component ratio) of the unpeeled product. The waveform processing unit 12 performs the Fourier transform of the FID signal of the copolymer 5 polymer obtained by NMR, and # The processing of the NMR spectrum is performed at the same time as the processing described in the known sample, and the NMR spectrum signal of the unknown sample is generated. Signal processing is similarly performed by the sample analysis unit 15 The chemical shift of the leaf transform is aligned with the phase alignment of the NMR spectral signal containing the waveform, the baseline processing, the peak integration, and the chemical shift value (normalization) that becomes the reference. Here, the range of chemical shifts is used to include the constituent polymer. The range of the observation nucleus of each constituent unit. However, the sample analysis unit 15 quantizes the number of the moments including the chemical shift and the signal intensity as (4) as the following formula (9) = Quantitative use information is an unknown sample. 3 (m=3) :: 二吏: Information 'But no matter if the unknown sample is one or more, all enter [6] n63⁄43⁄4 !_ 1 li

p p P 刀竹部 料中讀出加權向量 子；儲存部16内的才 丨隹丨j至％〜加權向蜃 出說明變量(NMR㉝)側的心〔二 Λ Τp p P The weight vector is read from the bamboo material; the value in the storage unit 16 is 至j to %~weighted to the heart of the explanatory variable (NMR33) side [二Λ Τ

Awl (Wiw/) '&quot;2 〜Ui 73 201222146 *r\j^〇oyii J — [An 然後，樣品分析部15讀出儲存於儲 由模型生成部14所求出的内部相闕係數子部16内的已藉 數sn，並根據以下的式求出目標變量 ^〜内部相關係 分率）側的分數（向量）UAl〜分數體的二單元組 里）UAn 。 UA1 = SjtA1 UAn — SntAn 繼而，樣品分析部使用儲存於 由模型生成部14所求出的向量 円的已藉 本山u -·丄 qi向量qn，由如上述般 率（向量）^〜三單元时车早⑽三單元組分 為三巧組》率的酬值而輪出。該三單元組分率（向量） IT。了二單^，率（向里）〜表示3個未知試樣各自的n 個平體單元的每-個的三單元組分率的賴值（三單元組 分率預測值）。 CAi = uAiqi CAn ~ ^Αη^η 201222146 ^tu^oopif 個的然控乂部18將各未知試樣的n個單體單元的每一 ^的二早讀分率預難製成結果表，並顯示於顯示部17 根據上述本實施形態的共聚合物評價方法，由於 樣Γ施加不必要的熱’因此能如高精度預測共聚合物的Awl (Wiw/) '&quot;2 to Ui 73 201222146 *r\j^〇oyii J - [An, the sample analysis unit 15 reads out the internal phase coefficient subsection obtained by the storage model generating unit 14 The borrowed number sn in the 16th, and the score (vector) of the target variable ^~ internal phase relationship fraction) is obtained according to the following formula: UAl to the second unit of the fractional body) UAn. UA1 = SjtA1 UAn - SntAn Then, the sample analysis unit uses the borrowed Ben u -·丄qi vector qn stored in the vector 求出 obtained by the model generating unit 14 from the above-described rate (vector) ^ to three units The car's early (10) three-unit component is rounded out for the value of the tripartite group. The three-unit component rate (vector) IT. The ratio (inward) to the ratio of the three-unit component rate of each of the n flat-body units of the three unknown samples (predicted by the three-unit component ratio). CAi = uAiqi CAn ~ ^Αη^η 201222146 ^tu^oopif control unit 18 pre-difficult to read the second early reading rate of each of the n monomer units of each unknown sample, and Displayed on the display unit 17 According to the copolymer evaluation method of the present embodiment described above, since the sample is subjected to unnecessary heat, it is possible to predict the copolymer as high precision.

、减=的構賴共聚合_單財元各自的三單元組 (二單元組分率預測值）。 通常，半導體微影製程用組成物中所使用的溶劑缺乏 對於均聚物的溶解性，因此推測相_構成單元連接而成 的聚合鏈會使對於溶劑的溶解性惡化。 只際上，如後述的實例所示般，若共聚合物鏈中所含 有的各個同一種類的單體單元的三單元組分率少，則妓聚 合物對於溶劑的溶解性提昇，並且含有該共聚合物的^蝕 劑組成物對於所照射的光的感光度提昇。 關於感光度，推測若共聚合物鏈中所含的各個同一種 類的單體單元的三單元組分率少，則即便單體單元為相同 比例，單體（構成）單元亦更均勻地分布於各共聚合物鏈 中。因此，當使用同一種類的單體單元的三單元組分率少 的共聚合物生成抗敍劑組成物時，可認為抗餘劑組成物對 於所照射的光具有高感光度。 根據以上的理由，本發明的實施形態的共聚合物評價 方法可簡便地評價構成共聚合物的單體的鏈結構的無規 性’關於含有概況聚合物的抗蝕劑組成物（微影製程用組 75 201222146 成物）的特性，可實際上不製備 =r得的共聚合物中的同-=4= 光:評價自該共聚合物所製備_劑組成物 再者’共聚合物射所含有的各 的分率可藉”讀絲㈣。早兀-早凡，，且 欲‘物的合成中的各單體的使用量是對應於 合2===::決定’且以使合成後的共聚 聚合條件接相目標的單體域的方式設定 但是’於多數情況下’進行共聚合的單體的丑聚 互不相同，因此不無規地進行絲合 =的單體(單元)组成產生差異，並且其共聚 偏^。另外，根據本發明者等的發現，所獲得的共聚合 的早體組成亦會因反應時間（聚合率）的不同而產生^ 不其於聚合反應的初期及後期，單體組成與目標值大 合_共==成含有許多相同的構成單元連接而成的聚 因此’例如如後述的實例所示般，若㈣上述聚合方 / ^Zi)或聚合方法（Z2)，較佳為部分滴加方式，以於 =反應的初期、絲妓應的減紐期，使所生成的 =合物的單體組成關差變小的方式進行㈣，則食不 亥控儀情況概，單體單元的三單元組分率的預測 H聚合物對於溶劑的溶解性、及含有該共聚合物 201222146 wzoopif 的抗蝕劑組成物的感光度提昇。 更佳為使用上述微影製程用聚合物的製造方法的實施 形態（Z2，），以於聚合反應的初期與後期，使所生成的共 聚合物的單體組成的偏差變小的方式進行控制。 具體而言，較佳為藉由本實施形態的共聚合物評價方 法所算出的單體單元的三單元組分率（三單元組分率預測 值）的合計於共聚合物中為2〇莫耳％以下的微影製程用共 • 聚合物。該三單元組分率的合計更佳為15莫耳。/。以下，進 而更佳為13莫耳％以下。 δ亥二單元組分率的合計為上述範圍的微影製程用共聚 合物對於溶劑的溶解性優異，並且可形成高感光度的抗蝕 膜。 因此，可容易且良好地進行製備抗蝕劑組成物時的聚 δ物對於抗钮、洛劑的溶解。另外，抗蚀劑組成物可獲得對 於驗性顯影液的優異的溶解性，有助於感光度的提昇。另 外，因抗蝕劑組成物中的不溶物少，故於形成圖案時，不 易產生起因於該不溶物的缺陷。 因此，藉由使用該抗蝕劑組成物製造形成有圖案的基 板可於基板上穩定地形成缺陷少且高精度的微細的抗餘 圖案。另外，亦可較佳地用於藉由如下的微影製程實現的 圖案形成，該微影製程是要求使用高感光度及高解析度的 Ϊί劑組成物且利用波長250 -以下的曝光用光的ί微 衫I程或電子束微影製程，例如是使用ArF準分子雷射 (193 nm)的微影製程。 刀田' 77 201222146 再者，當製造利用波長250 nm以下的曝光用光ό勺光 微影製程中所使用的抗蝕劑組成物時，較佳為以使聚合物 於該曝光用光的波長中為透明的方式來適宜選擇單體。 &lt;共聚合物組成分析方法（鏈結構的無規性的推斷） &gt; 圖2是表不利用本發明的一實施形態的共聚合物組成 分析方法的進行共聚合物中的單體單元的排列狀態的分析 的共聚合物組成分析裝置的構成例的概略方塊圖。 共聚合物組成分析裝置具備用以使共聚合物中的單體 單元的湖狀㈣共聚合物組成分析方法巾❹的電腦執 仃的以下雜式。姉式是用以使電職行如下處理的程 式：測定資料提取的處理’測定資料提取部自上述共聚合 物的NMR光譜’將包含構成上述共聚合物的上述單體各 自的波長的範目的NMR光譜作為共聚合_定資料而提 $，主成分分析的處理’域分分析部進行對於上述 in料、及上述單體各自的麵光譜的單體；定 貝枓的化學轉及賴岐社絲 述單，數量n(n為2以上的整數）的第 距離异出的處理，數值轉換部求出在上述第丨主成分至 1主成分的域分軸所構成的n _域分空 成分軸中的上述單體的主成分得分所表示ί 維的啸如，至上述共聚合物的主成分得 對象座標點為止的評價距離;以及特性評價的 寺性㈣部藉由上述評價距離而評價上述共聚合物 78 201222146 HWZOOpif 的特性。 具體而s，本實施形態的共聚合物組成分析裝置31 包括：波形處理部311、主成分分析部312、數值轉換部 313、特性評價部314、NMR資料儲存部315及主成分資 料儲存部316。The structure of the subtraction = co-aggregation _ single fiscal unit three-unit group (two-unit component rate prediction value). In general, since the solvent used in the composition for a semiconductor lithography process lacks solubility in a homopolymer, it is presumed that the polymer chain in which the phase-constituting unit is connected deteriorates the solubility in a solvent. In the meantime, as shown in the example described later, if the triad component ratio of each of the same type of monomer units contained in the copolymer chain is small, the solubility of the ruthenium polymer to the solvent is improved, and the The sensitivity of the composition of the copolymer to the irradiated light is increased. Regarding the sensitivity, it is presumed that if the triad component ratio of each of the same type of monomer units contained in the copolymer chain is small, even if the monomer units are in the same ratio, the monomer (constituted) units are more uniformly distributed. In each copolymer chain. Therefore, when a synthase composition having a small triad fraction of the same type of monomer unit is used to form an antinarrant composition, it is considered that the anti-reagent composition has high sensitivity to the irradiated light. For the above reasons, the copolymer evaluation method according to the embodiment of the present invention can easily evaluate the randomness of the chain structure of the monomer constituting the copolymer 'with respect to the resist composition containing the polymer (the lithography process) With the characteristics of group 75 201222146, it is possible to actually prepare the same -=4= light in the copolymer obtained by =r: evaluation of the composition of the composition prepared from the copolymer and then the 'copolymer shot Each of the fractions contained can be referred to as "reading silk (4). Early in the morning - early, and the amount of each monomer used in the synthesis of the object corresponds to the combination of 2 ===::" The copolymerization polymerization conditions after the synthesis are set in the manner of the monomer domains of the target phase, but the ugly polymerization of the monomers which are copolymerized in many cases is different from each other, so that the monomer of the silk-bonding = unit is not randomly In addition, according to the findings of the present inventors, the composition of the obtained copolymerized early body is also caused by the difference in reaction time (polymerization rate), which is not in the polymerization reaction. In the initial stage and the later stage, the monomer composition is in agreement with the target value. There are many aggregates in which the same constituent units are connected. Therefore, for example, as shown in the examples described later, if (4) the above-mentioned polymerization side / ^Zi) or the polymerization method (Z2), it is preferable to partially add a method to = reaction In the initial stage, the silkworm should be reduced in the period of time, so that the monomer composition of the formed compound is reduced in a small manner (4), the case of the food control device is small, and the unit cell ratio of the monomer unit is It is predicted that the solubility of the H polymer in the solvent and the sensitivity of the resist composition containing the copolymer 201222146 wzoopif are improved. More preferably, the embodiment using the above-described method for producing a lithography process polymer (Z2,) In the initial stage and the later stage of the polymerization reaction, the variation in the monomer composition of the produced copolymer is controlled to be small. Specifically, it is preferably calculated by the copolymer evaluation method of the present embodiment. The triad component ratio (predicted value of the triad component ratio) of the monomer unit is a total of 2 〇 mol% or less of the lithographic process co-polymer in the copolymer. The total ratio of the three unit components is More preferably 15 moles. In addition, it is more preferably 13 mol% or less. The eutectic composite copolymer having the above-mentioned range is excellent in solubility in a solvent, and a high-sensitivity resist film can be formed. Therefore, the dissolution of the poly-δ substance in the preparation of the resist composition for the anti-button and the dying agent can be easily and satisfactorily obtained. In addition, the resist composition can obtain excellent solubility for the developer solution, which is helpful. In addition, since the insoluble matter in the resist composition is small, defects due to the insoluble matter are less likely to occur when the pattern is formed. Therefore, the resist composition is used to manufacture and be formed. The patterned substrate can stably form a fine residual pattern with few defects and high precision on the substrate. Further, it can also be preferably used for pattern formation by the following lithography process, which is required to be used. High-sensitivity and high-resolution 组成 composition and use of exposure light with a wavelength of 250 Å or less, or electron beam lithography, such as lithography using ArF excimer laser (193 nm) Process. Knife Farm ' 77 201222146 Furthermore, when manufacturing a resist composition used in an exposure light lithography process using a wavelength of 250 nm or less, it is preferable to make the polymer at the wavelength of the exposure light. The medium is transparent to suit the monomer selection. &lt;Commerce composition analysis method (inference of randomness of chain structure) &gt; Fig. 2 is a view showing a monomer unit in a copolymer which is analyzed by a method for analyzing a copolymer composition according to an embodiment of the present invention. A schematic block diagram of a configuration example of the copolymer composition analysis apparatus in the analysis of the arrangement state. The copolymer composition analysis apparatus is provided with the following formula for the computer configuration of the lake-shaped (tetra) copolymer composition analysis method for the monomer unit in the copolymer. The 姊 formula is a program for causing the electric job to process the following: a process of measuring data extraction 'the measurement data extraction unit from the NMR spectrum of the above-mentioned copolymer' will contain the wavelength of each of the above-mentioned monomers constituting the above-mentioned copolymer. The NMR spectrum is evaluated as a copolymerization data, and the process of principal component analysis is performed by the domain analysis unit for the above-mentioned in-situ and the surface spectrum of each of the monomers; the chemical conversion of Dingbei and the Laiwu Society The processing of the first distance of the number n (n is an integer of 2 or more), and the numerical conversion unit obtains the n _ domain separation component composed of the domain minor axis of the first principal component to the first principal component. The principal component score of the above-mentioned monomer in the axis indicates the evaluation distance from the coordinate point of the principal component of the copolymer, and the temple (four) portion of the property evaluation is evaluated by the evaluation distance. The characteristics of the above copolymer 78 201222146 HWZOOpif. Specifically, the copolymer composition analysis apparatus 31 of the present embodiment includes a waveform processing unit 311, a principal component analysis unit 312, a numerical value conversion unit 313, a characteristic evaluation unit 314, an NMR data storage unit 315, and a principal component data storage unit 316. .

波形處理部311進行自NMR測定部350所輸入的共 聚合物或聚合物的FID ( Free Induction Decay )信號的傅 里葉變換及資料處理，並對每個樣品賦予樣品識別資訊， ，將包含化學位移量（頻率成分）及每個化學位移量的光 譜強度的NMR光譜資料與樣品識別資訊一同寫入、儲存 於NMR資料儲存部315中。 f冗肘巴含稱成評價對象的共聚合物或聚合4 的僅包含各單體的均聚物的化學位移量及每個化學位心 的光譜強度的NMR光譜、與各解賴射訊^ =NMR資料儲存部315中。另外，與評價對象的; ♦。=同樣地’波形處理部311亦可根據測定部^ 疋的均㈣的刪!^飾生成觀&amp;光譜資料，並3 其與各個單體識別資訊—同儲存。 户从,成刀分析部312進行NMR資料儲存部315中所々 Z白二個樣品的主成分分析’並針對每個樣品’將主成; 絲〜主成分得分於域分資料儲存部316中寫入至相3 -、母個樣品識別資訊、每個單體識別資訊中。 分’主成分分析部312於主成分分析中，針對主; 的數4 ’即域分數，按㈣得的域分之中貢ΙΜ 79 201222146 由高至低社成分的财，僅 合物的單體的種類的數量。 二= 的單體的種類的數量相同㈣㈣共聚合物 該單體__數量相同。社成分空關維數亦與 共聚==:r;:=r_生成的 自貢===3個主成分作為主成:== W八,13將在由各主成分的主成分轴所形成的 二刀:=’評價對象的共聚合物的各主成分軸中的主 點’即主成分空間中的評價對象的共聚 13 V點與包括所有僅包含1種單體的均聚物的樣品 的座標的空間的距離作為評價距離而求出。此處，所謂主 成分空間’是指包含_自_域分分析賴得的主成 分的η (2^η)個主成分相對應的相互直行的域分軸的 空=。該主成分空間的座標點成為將各主成分轴的主成分 得分作為座標值，且由η個主成分軸的座標值所示的11維 空間中的座標的點。 例如’圖3是表示顯示對使3種單體進行聚合而生成 的共聚合物所進行的主成分分析的結果的三維的主成分空 間中的各樣品的座標點的圖。 於使用3種單體，且主成分數為3個的情況下，主成 分空間成為三維，於該三維空間中，3種單體的3個座標 點形成二維平面（二維空間）q作為比較空間。即，作為 201222146 包含全部3種單體的座標點P fΔ，、—The waveform processing unit 311 performs Fourier transform and data processing of the FID (Free Induction Decay) signal of the copolymer or polymer input from the NMR measuring unit 350, and imparts sample identification information to each sample, and contains the chemical The NMR spectrum data of the displacement amount (frequency component) and the spectral intensity of each chemical shift amount are written together with the sample identification information and stored in the NMR data storage unit 315. f redundant elbow contains the copolymer of the evaluation object or the chemical shift amount of the polymer 4 containing only the monomer, and the NMR spectrum of the spectral intensity of each chemical center, and each of the solutions = NMR data storage unit 315. In addition, with the evaluation object; ♦. In the same manner, the waveform processing unit 311 can generate the viewing & spectral data based on the deletion of the measurement unit (4), and store the same with the individual identification information. The mastering analysis unit 312 performs the principal component analysis of the two samples of the 白Z white in the NMR data storage unit 315 and generates the main component for each sample; the silk to principal component score is written in the domain data storage unit 316. Into the phase 3 -, the mother sample identification information, each monomer identification information. In the principal component analysis section 312, in the principal component analysis, the number of 4', that is, the domain score, and the domain score obtained by (4) are among the points of the contributor 79 201222146 from the high to the low social component, the only compound The number of types of bodies. The number of the two types of monomers is the same (four) (four) copolymer The number of monomers __ is the same. The compositional dimension of the community is also associated with the copolymerization ==:r;:=r_ generated by Zigong ===3 principal components as the main component: == W8, 13 will be formed by the principal component axis of each principal component The second knife: = 'the main point in each principal component axis of the copolymer of the evaluation object', that is, the copolymerized 13 V point of the evaluation object in the principal component space and the sample including all the homopolymers containing only one monomer The distance of the space of the coordinates is obtained as the evaluation distance. Here, the principal component space 'is an empty null of the mutually orthogonal domain sub-axis corresponding to the η (2^η) principal components of the main component to which the _ self-domain analysis is based. The coordinate point of the principal component space is a point of a coordinate in the eleven-dimensional space indicated by the coordinate value of the n principal component axes, which has the principal component score of each principal component axis as a coordinate value. For example, Fig. 3 is a view showing coordinate points of each sample in a three-dimensional principal component space as a result of principal component analysis performed on a copolymer produced by polymerizing three kinds of monomers. When three types of monomers are used and the number of principal components is three, the principal component space becomes three-dimensional, and in the three-dimensional space, three coordinate points of the three kinds of cells form a two-dimensional plane (two-dimensional space) q as Compare space. That is, as 201222146, the coordinate points P fΔ, including all three kinds of monomers, are included.

座標點Ρ(Α-3)的空間，自該3偏主4示'點Ρ (Α_1)、 作為比較空間。 纟2個座標點形成二維空間Q 另外’數值轉換部313算出作為 的於三維空間中的座標點P (s)、 ^象的-聚口物 成的二維的比較空間Q的評價距離;⑻體== 換部313所進行的評價距離L(s)的算^= 轉 特性評價部314根據包含所有 仃洋述 評價，聚合的= ”規性’並根據該判定結果進行評價 影製程特性的評價’且將結果輸出至未圖示的 使財實麵'齡的絲合物㈣ :的評價方法謝物組成分析方法)包：： 中，進，舰影製朗共聚合物溶解於溶劑 行）進H „物的NMR败（於NMR峡部350中進 的形P處理過程，進行藉由測定過程⑴所獲得 處理號的傅里葉變換及資料處理(於波形 81 1 主成分分析過程，對各樣品進行自波形處理過程 2 斤輸出的NMR光譜資料的定量使㈣訊的主成分分 201222146 析’算出所選擇的主 成分分析部312中進行）；的樣品的主成分得分（於兰 (4)數值轉換過程，八 抽’即叫體的種類數作為維=:，種類數的主成分 述過程（3)所輸出的各主成分分空間中，將自上 的座標轴（主成分轴）上=成为得分於直行的不同 各座標轴（主成分轴）的f表不為座標值，另外，由 各樣品於主成分空間中的位f f成分得分〕表示作為 聚物的主成分得分所表示古上標點’算出作為通過均The space of the coordinate point Α(Α-3), from the 3 partial main 4 shows 'point Ρ (Α_1), as a comparison space.纟 two coordinate points form a two-dimensional space Q. Further, the 'value conversion unit 313 calculates an evaluation distance of the two-dimensional comparison space Q which is the coordinate point P (s) in the three-dimensional space and the merging material of the image. (8) Body == The calculation of the evaluation distance L(s) by the change unit 313 is performed by the conversion characteristic evaluation unit 314 based on the evaluation of all the foreign language evaluations, and the evaluation process is performed based on the judgment result. 'Evaluation' and output the result to a non-illustrated silk-solid compound (fourth): evaluation method of the composition of the composition)::,,,,,,,,,,,,,,,,,,,,,,, )) NMR of the H „ object (the shape P process in the NMR isthmus 350, performing the Fourier transform and data processing of the process number obtained by the measurement process (1) (in the waveform 81 1 principal component analysis process, For each sample, the NMR spectrum data of the 2 kg output from the waveform processing process was quantified, and the principal component of the (4) signal was analyzed in 201222146 to calculate the principal component score of the sample (in the selected principal component analysis unit 312); 4) The process of numerical conversion, eight pumping The number of types is defined as dimension =:, in the principal component subspace in which the principal component description process (3) is output, the coordinate axis (main component axis) from the top is set to be a different coordinate axis for the straight line ( The f-table of the principal component axis) is not a coordinate value, and the score of the bit ff component in the principal component space of each sample indicates that the ancient punctuation as the principal component score of the polymer is calculated as

品所表示的座標點的距離的評的比較空間與各樣 中進行）； 知距離（於數值轉換部313 (5)特性評價過程，藉由上 算出的通過均聚物的主成分尸八^ 〜（4)過程中所 較空間與各樣品所絲的^财座標點的比 影製程用共聚合物的組成物的微旦貝評價含有上述微 部3U中進行）。 物的微影製程特性（於特性評價 於本實施形態令，較佳為The comparison space of the evaluation of the distance of the coordinate point indicated by the product is performed in each of the samples; the known distance (in the characteristic evaluation process of the numerical value conversion unit 313 (5), the principal component of the homopolymer is calculated by the above calculation. The ratio of the space in the process to the (4) process and the particle size of each sample is determined by the micro-damp evaluation of the composition of the copolymer for the process containing the above-mentioned micro-part 3U. The lithography process characteristics of the object (in the evaluation of the characteristics, it is preferably

述評價距離來評價在上述共聚人平價部314根據上 述單體連續地配置的長度。A 、、’且成中同一種類的上 距離=限«欺上述評價 較，來㈣㈣上料 82 201222146 40288pif 價包括對於溶劑的溶解性及曝光中的感光度的微影製程特 性。 、 作為用於NMR測定的NMR測定部350的襞置，只要 使用市售品即可，並無特別限定。但是，就化學位移的解 析度高的觀點而言，較佳為使用磁場強度為7特士拉（作 為1Η核的頻率為3〇〇MHz)以上的NMR裝置。The length of the above-described copolymerization unit 314 which is continuously arranged in accordance with the above-described monomers is evaluated by the evaluation distance. A,, and the upper distance of the same type = limit «deception of the above evaluation, compared to (four) (four) loading 82 201222146 40288pif price includes the lithography process characteristics for solvent solubility and sensitivity in exposure. The NMR measurement unit 350 for NMR measurement is not particularly limited as long as it is a commercially available product. However, from the viewpoint of a high degree of resolution of the chemical shift, it is preferred to use an NMR apparatus having a magnetic field strength of 7 tesla (3 〇〇 MHz as a frequency of 1 Η nucleus).

NMR測定中的觀測核只要對應於共聚合物（p)的種 類而適宜選擇即可，但就相對同位素豐度或感光度 點而言，較佳為1H、13C、19F、29Si。 用於NMR測定的樣品管的直徑只要對應於共聚合物 (P)的種類而適宜選擇即可’當選擇iH、作為觀測核 時，就相對同位素豐度高的觀點而言，較佳為3 mm(p以 上，更佳為5 mmcp以上。另外，當選擇、29&amp;作為觀 測核時，肪獲得靈敏度更高的信號強度的觀點而言，較 佳為5mm(p以上，更佳為1〇mm(p以上。 用於NMR峡的絲合物的&amp;化溶射的試樣濃度 2特別限定’但就可獲得紐度更高的錢強度的觀點 S ’較佳為1質量％以上，另外，更佳為5質量％以上， 進而更佳為10質量％以上。 另外’就抑制輯樣溶液的黏度造成的緩和時間的影 a的觀點而言，較佳^ @ θη/ 平又住马50 I 以下，更佳為30質量％ 以下，進而更佳為20質量％以下。 則* Ζ &amp; NMR翁m、要可使絲合物溶解， 、並無特舰定，例如可列舉H氣仿（CDC13)、氣化 83 201222146 二甲基亞硬（DMS〇-d6)、氧化氣（d2〇)、氣化曱醇（CH3〇d 或cd3od)、說化六氟異丙醇（HFIP_d2)等。另外，亦可 添加四曱基魏（TMS)或沉13作為化學位移的基準物 質。 N MR，則定時的試樣，溫度只要是試樣溶劑的沸點以 下、或者不產生共聚合物的分解或變質的溫度，則並無特 別限定，但就可獲得靈敏度更高的信號強度的觀點而;， 較佳為儘可能為高溫。 NMR測定時的資料累計次數並無特別限定，只要對應 於所測定的觀測核的種類而適宜選擇即可，當選擇4、!&amp; 作為觀測核時，就相對同位素豐度高的觀點而言，較佳為 4次以上，更佳為16次以上。另外，當選擇i3c、作 為觀測核時，就可獲得靈敏度更高的信號強度的觀點而 言，較佳為1500次以上，更佳為3000次以上，此處，所 謂NMR測定時的累計，是指多次獲取NMR信號，使該多 次的信號重疊（或者累計或相加）’並將該經重疊的信號作 為最終的試樣的觀察結果的FID信號。 波形處理部311於波形處理過程中，如已說明般，進 行藉由NMR測定所獲得的HD信號的傅里葉變換，生成 具有化學位移（頻率成分）及信號強度（光譜強度）的資 訊的NMR光譜資料。 此時’對應於所測定的觀測核的種類，設定BF (擴張 因數）（事先於實驗中進行測定，然後設定對應於各個觀^ 核的擴張因數），藉此可提昇所對應的觀測核的光譜解析 84 201222146 度，因此可提昇測定精度。 與包::波光 纖嶋糊使各個職 譜信號的基線與頻率軸平行的方式進行校正/= 移值的設定，並輸出包含以規定的範圍 位移而成的頻率細、及於每個 U化子The observation nuclei in the NMR measurement may be appropriately selected as long as they correspond to the species of the copolymer (p), but are preferably 1H, 13C, 19F, and 29Si in terms of relative isotope abundance or sensitivity. The diameter of the sample tube used for the NMR measurement can be appropriately selected as long as it corresponds to the type of the copolymer (P). When iH is selected as the observation nucleus, it is preferably 3 from the viewpoint of high isotopic abundance. Mm (p or more, more preferably 5 mmcp or more. In addition, when selecting, 29 &amp; as the observation nuclei, from the viewpoint of obtaining a signal intensity with higher sensitivity, it is preferably 5 mm (p or more, more preferably 1 〇). Mm (p or more. The sample concentration 2 for the &lt;melting and solvating of the NMR gorge is particularly limited to 'there is a viewpoint of obtaining a higher strength of the kinetic energy, S' is preferably 1% by mass or more, and More preferably, it is 5% by mass or more, and more preferably 10% by mass or more. Further, from the viewpoint of suppressing the shadow a due to the viscosity of the sample solution, it is preferable that ^@θη/平和马马50 I is more preferably 30% by mass or less, and still more preferably 20% by mass or less. Then * Ζ &amp; NMR can dissolve the silk compound, and there is no specific ship, for example, H gas imitation is mentioned. (CDC13), gasification 83 201222146 dimethyl subhard (DMS〇-d6), oxidizing gas (d2〇), gasification 曱(CH3〇d or cd3od), hexafluoroisopropanol (HFIP_d2), etc. In addition, tetradecyl-Wei (TMS) or sinker 13 may be added as a reference material for chemical shift. N MR, timed sample The temperature is not particularly limited as long as it is at least the boiling point of the sample solvent or does not cause decomposition or deterioration of the copolymer. However, from the viewpoint of obtaining a signal intensity with higher sensitivity, it is preferable to The number of times of accumulation of data in the NMR measurement is not particularly limited, and may be appropriately selected in accordance with the type of the observed nuclear nucleus. When 4, !&amp; is selected as the observation nucleus, the relative isotope abundance is high. In view of the above, it is preferably 4 or more, and more preferably 16 or more. Further, when i3c is selected as the observation core, it is preferable to obtain a signal intensity with higher sensitivity, preferably 1500 or more. More preferably, it is 3,000 or more times. Here, the accumulation in the NMR measurement means that the NMR signal is acquired a plurality of times, and the plurality of signals are superimposed (or accumulated or added)' and the superimposed signals are finally used. Observation of the sample The FID signal of the fruit. The waveform processing unit 311 performs Fourier transform of the HD signal obtained by NMR measurement to generate chemical shift (frequency component) and signal intensity (spectral intensity) during waveform processing. NMR spectral data of the information. At this time, BF (expansion factor) is set corresponding to the type of the observed nuclear nucleus (measured in advance in the experiment, and then the expansion factor corresponding to each nucleus is set) The spectral analysis of the corresponding observation nuclei can be improved by 84 201222146 degrees, so the measurement accuracy can be improved. And the package::wave fiber paste makes the baseline of each spectrum signal parallel to the frequency axis to correct/= shift value setting, and output the frequency including the displacement of the specified range, and each U child

::積分所得的值_光譜資; 使用包含構成評價對象的共聚合物二 =;=圍 核的範圍。即，波形處理部3 冓成早几的觀測 輸入的NMR光级中由_測定部所 合物的所有單體中曰二、薄2包含構成評價對象的共聚 譜，然後進行NMR光譜錢的=頻率範圍的職R光 態的====，在本實施形 葉變換接祕風“ 〃積+瞻在於用以進行傅里 割化學位移；率的=谱強度的積分的頻率範圍’即分 訊，Γ 根據樣品識別資訊或軍體識別資 均聚物的樣品的ΝΜΓ=二:讀出=共聚合物及 物=====資料作為共聚合 例如’波形處理部311針對m種共聚合物或均聚物的 85 201222146 ^Τν^,〇〇ρχΑ 樣品中的第k個樣品（k為1〜m的整數），以固定的間隔 將化學位移（頻率範圍）分割成P等分（p為整數）的頻 率範圍，並將所分割的頻率範圍的第g個的積分值設為 fkg。如此，波形處理部311進行自m種共聚合物及均聚物 的樣品的NMR光譜，生成共聚合物及均聚物的樣品的各 個NMR光譜資料的處理。 此處，均聚物是包含構成評價對象的共聚合物的單體 中的同一種類的單體的聚合物。因此，當評價對象的共聚 合物包含η種單體時，由於以均聚物計達到11種，因此變 成m&gt;η的關係。 另外:: Values obtained by integration _ spectrometry; use a range containing the co-polymers that constitute the evaluation object =; = enclosure. In other words, in the NMR light level of the observation input which is formed by the waveform processing unit 3, the copolymerization spectrum of the evaluation target is included in all the monomers of the composition of the measurement unit, and then the NMR spectrum is used. In the frequency range of the position R state ====, in this embodiment, the shape change is connected to the secret wind "hoarding + view is used to carry out the chemical shift of the Fourier cut; the rate = the frequency range of the integral of the spectral intensity" Γ, Γ According to the sample identification information or the sample of the military identification homopolymer, ΝΜΓ=2: read=copolymer and substance===== data as a copolymerization, for example, 'waveform processing unit 311 for m kinds of copolymerization Or the homopolymer of 85 201222146 ^Τν^, 〇〇ρχΑ The kth sample in the sample (k is an integer from 1 to m), and the chemical shift (frequency range) is divided into P aliquots at regular intervals (p In the frequency range of the integer), the integral value of the gth of the divided frequency range is fkg. Thus, the waveform processing unit 311 performs NMR spectroscopy of samples from m kinds of copolymers and homopolymers to generate a total of Treatment of individual NMR spectral data of samples of polymers and homopolymers. The material is a polymer of the same type of monomer among the monomers constituting the copolymer of the evaluation target. Therefore, when the copolymer of the evaluation target contains η kinds of monomers, since 11 kinds of homopolymers are used, Therefore, it becomes the relationship of m> η.

波形處理部311針對共聚合物及均聚物的每艰 樣品，使分割化學位移而成的頻率範圍内的光譜強度（信 號強度）的積分值於所有經分割的頻率範圍内相加，並^ 該相=的合計設為議，⑭以下的 率範圍_積分值的鮮b 谷哭 fkl + fk2+…fkg+…+ fkp=iooThe waveform processing unit 311 adds the integrated value of the spectral intensity (signal intensity) in the frequency range in which the chemical shift is divided for each difficult sample of the copolymer and the homopolymer in all the divided frequency ranges, and The total of the phase = is set as the discussion, the rate range below 14_the value of the fresh b valley cry fkl + fk2+...fkg+...+ fkp=ioo

類 fg-ave- ^flg+f2g+-fkg+- + f )/m 86 201222146 πυζδδριί 光譜經ρ等分的頻率範圍(分割 對第的射求紅辭均值後，針Class fg-ave- ^flg+f2g+-fkg+- + f )/m 86 201222146 πυζδδριί The frequency range of the spectrum by ρ aliquot (divided after the average of the first shot red word, the needle

内，自經標準化的光;強产=f=每個頻率範圍 結果作為經基準化的積分值、心:以=: ave bkg=fkg-fg. ，後’波形處理部311將第k個樣品的經測定的頻率 ΝΛΓ固分魏域的光譜強度設為由下式的向量所表示的 光譜資料。 xk= (bkl、bk2、…、bkg、…、bkp) 然後’波形處理部311彙集關於所有m種樣品的光譜 蛋度，並由以下的（31)式的矩陣g表示。該（31)式所 「的矩陣G (m列p行）成為變成生成說明變數的基礎的 /匕學位移及信號強度（積分後）。如後述般，對矩陣G進 行主成分分析，並製作説明變數的矩陣T。 [數7] 87 • * - (31) 201222146 f Λ ^Internal, self-normalized light; strong yield = f = each frequency range result as a benchmarked integral value, heart: = ave bkg = fkg - fg., after 'waveform processing section 311 will kth sample The measured frequency of the measured enthalpy is determined by the spectral data represented by the vector of the following formula. Xk = (bkl, bk2, ..., bkg, ..., bkp) Then, the waveform processing unit 311 collects the spectral egg degrees for all m kinds of samples, and is represented by the matrix g of the following formula (31). The matrix G (m-column p-row) in the equation (31) is a drop-out displacement and a signal intensity (after integration) which are the basis for generating the explanatory variables. As will be described later, principal component analysis is performed on the matrix G, and is produced. Describe the matrix T of the variables. [7] 87 • * - (31) 201222146 f Λ ^

若自波形處理部311供給矩陣G，則主成分分析部312 生成該矩陣G的轉置矩陣GT (p列m行）。 然後，主成分分析部312針對矩陣G，自左側乘以所 求出的轉置矩陣GT，而求出乘積矩陣gtg。 繼而，主成分分析部312藉由以下的關係式而求出所 求出的乘積矩陣GTG的固有向量v。 GTGV = Δ2Υ 此處所求出的固有向量v 固有值…叫由以下的⑼式表^ 表不 [數8]When the matrix G is supplied from the waveform processing unit 311, the principal component analysis unit 312 generates the transposed matrix GT (p columns and m rows) of the matrix G. Then, the principal component analysis unit 312 multiplies the obtained transpose matrix GT from the left side with respect to the matrix G to obtain a product matrix gtg. Then, the principal component analysis unit 312 obtains the eigenvector v of the obtained product matrix GTG by the following relational expression. GTGV = Δ2Υ The eigenvector v eigenvalue obtained here is called the following (9) formula ^ Table [No. 8]

«11 ίαρΐ Ρ ΡΡ (32) [數9] 88 201222146 HU^OOpif Δ2： λ1 * » λ ΡΑ (33) 另外，（32)式的V具有以下的關係 2 { (an) 2+ (a2i) 2H-----l· (api) 1/2. ^-----· (ap2) 2} 2Λ l/2_ 1 l/2 { (al2) 2+ (a ) {(alp)2+ (a2p)2 + ...+ \ ^pp ) 另外，於（33)式的Δ2中，λ^λγ...、）3 陣GTG的固有值，且。 疋乘積矩 而且，當要根據GTGV = W的關係式求 若Λ訂式的求㈣有值的定理來解3 多可獲付Ρ個解。該解之中，最大的人成為λι。 财 det (GTG^I) =：〇 是Ρ 大可求至λρ為止 =:固有值λ2是解λ之中第2大的1以下同樣最 ，主成分分析部祀將各個固有、…、 然後 人2、…、λρ 從而求出固有向量 代入GTGV^V的關係式的λ來解式， V。 89 201222146 繼而，主成分分析部312針對矩陣G (彙集了關於所 有η種樣品的光譜強度的矩陣），如以下所示自右側乘以所 求出的固有向量V，藉此可求出表示主成分得分（分數） 的矩陣Τ。«11 ίαρΐ Ρ ΡΡ (32) [Number 9] 88 201222146 HU^OOpif Δ2: λ1 * » λ ΡΑ (33) In addition, the V of the formula (32) has the following relationship 2 { (an) 2+ (a2i) 2H -----l· (api) 1/2. ^------(ap2) 2} 2Λ l/2_ 1 l/2 { (al2) 2+ (a ) {(alp)2+ ( A2p)2 + ...+ \ ^pp ) Further, in Δ2 of the equation (33), λ^λγ...,) is an inherent value of the matrix GTG.疋 Product moments Also, when you want to find the basis of GTGV = W, if you want to solve the problem, you can get a solution. Among the solutions, the biggest person becomes λι. Wet (et) is: 2, ..., λρ to obtain the λ of the relational vector of the eigenvectors into GTGV^V to solve the equation, V. 89 201222146 Then, the principal component analysis unit 312 multiplies the obtained eigenvector V from the right side with respect to the matrix G (a matrix in which the spectral intensities of all the η samples are collected), thereby obtaining the representation main A matrix of component scores (fractions).

GV = T 再者，矩陣T成為m列且最多p行的矩陣，由以下的 (34)式表示。 » 10] τ: : '· ； +、处 +…+ 〜〆*1/7 …bm\a\ p + bm2a2p + …+ bmpaPP - -· · (34) 而且，該矩陣T的第1行成為m種的各樣品中的第1 主成分PC1的主成分得分，第2行成為第2主成分PC2 的主成分得分^以下同樣最大可求至主成分PCn的主成分 得分為止。例如，作為第k個樣品的第1主成分得分的tkl 由以下的式表示。 tki —bkian + bk2ai2 Η-----^ bkpalp 另外，主成分分析部312將所求出的各樣品的主成分 201222146 4 ⑽ 8pif 儲存於主 得分與樣品識別資訊或單體識別資訊一同寫入 成分資料儲存部316中。 其次，對數值轉換過程的處理進行詳細說明 於=明’以下的說明列舉構成單元的單體為2種（^了更 :情=但單體的種類的數量並不特別限 ) 表不早體的種_數量的構成單元H 2’ Μ圖H表示橫軸為第1域分軸（PC1)，_為第2 的二維空間的主成分空間的圖：表 空間的二維空間。 又而構成的主成分 包含單體A]與單體A_2的 於二維空間的主成分空間少⑽維度二= 目對 而作為包含彼此的座標值的空間的比^空^間（射又）， 此處，數值轉換部313自主成分資‘二 藉由樣品識別資訊或單體識別資。 ， 元的丘喂人物S，β勿人-貝0孔而5貝出包含2個構成單 ^的八知物S &amp;包含早—的構成單 Α-卜樣品Α-2各自的第1主成 物的樣口口 第2主成分軸PC2料AΘ 1 的主成分得分與 弟2主成刀軸PC2駐成分4分，將 成分得分作為座標值，如下述般 成刀轴的主 的主成分空f种·標點。規4含該各域分得分 同樣地，評價對象的共聚合物的樣品 下述般規定。 叼尾知點亦如 P (A-l) = (PCI (A-l)，PC2 201222146 *tw^oopii P (A-2) = (PCI (A-2) ,PC2 (A-2)) P (S) = (PCI (S) ,PC2 (S)) 因樣品Α·1及樣品A-2是均聚物，故由聚合物的組成 中單一的構成單元完全連續地鍵結，即同一種類的單體不 包含其他種類的早體而連續地鍵結來構成。通過座標點p (A-1 )及座標點P ( A-2 )這2點的一維空間（作為比較 空間Q的線段）’即連結座標點P ( A-1 )與座標點p ( a-2) 的線段（直線）因作為構成單元的配置，相同的單體連續 地連結而配置，故其為單體的配置的連續性最高的線段。 自該線段的評價距離L(S)表示共聚合物中的鏈結構中的 單體的配置的無規性。 例如，數值轉換部313如下式般規定數值a、數值b、 數值c。 a=PC2 (A-2) -PC2 (A-1) b = PCl (A-1) -PCI (A-2) c = -PC 1 ( A-1 ) x ( PC2 ( A-2 ) -PC2 (A-1 ) ) -PC2 ( A-1 ) x (PCI (A-1) -PCI (A-2)) 92 201222146 nuz.oopif 1處’數值a表示第2主成分軸PC2上的樣品A 2與 7 \ 2之間的第2主成分得分的差量。數值b表示第j f f分軸PC1上的樣品A-2與樣品A-2之間的第i主成分 =刀的差星。數值c是使數值a乘以樣品A-1的第1主成 二付刀所待的結果的負的數值、與數值b乘以樣品A。的 第2主成分得分所得的結果的負的數值相加而成的值。GV = T Further, the matrix T becomes a matrix of m columns and at most p rows, and is represented by the following formula (34). » 10] τ: : '· ; +, at +...+ ~〆*1/7 ...bm\a\ p + bm2a2p + ...+ bmpaPP - -· · (34) Moreover, the first line of the matrix T becomes The main component score of the first principal component PC1 in each of the m kinds of samples, the second component becomes the principal component score of the second principal component PC2, and the maximum component can be obtained up to the principal component score of the principal component PCn. For example, tkl which is the first principal component score of the kth sample is represented by the following formula. Tki —bkian + bk2ai2 Η-----^ bkpalp Further, the principal component analysis unit 312 stores the principal component 201222146 4 (10) 8pif of each sample obtained in the main score together with the sample identification information or the single-digit identification information. The component data storage unit 316. Next, the processing of the numerical conversion process will be described in detail in the following description. The following descriptions show that the constituent units are two kinds of monomers (^: more: the number of the types of the monomers is not particularly limited). The number of constituent elements H 2 ' Μ H indicates that the horizontal axis is the first domain partial axis (PC1), and _ is the second principal space of the two-dimensional space: the two-dimensional space of the table space. Further, the main component is composed of a monomer A] and a monomer A_2 having a small principal component space in a two-dimensional space (10), a dimension of two, and a ratio of a space including a coordinate value of each other. Here, the numerical value conversion unit 313 determines the information by the sample identification information or the individual identification. , Yuan's Qiu feeds the character S, β 勿 人 - 贝 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 包含 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 The main component score of the second principal component axis PC2 material AΘ 1 of the sample mouth is 4 points, and the component score is used as the coordinate value. The main component of the main axis of the tool axis is as follows. Empty f species and punctuation. Rule 4 includes the scores of the respective domains. Similarly, the sample of the copolymer to be evaluated is defined as follows. The tail is also known as P (Al) = (PCI (Al), PC2 201222146 * tw ^ oopii P (A-2) = (PCI (A-2), PC2 (A-2)) P (S) = (PCI (S), PC2 (S)) Since the sample Α·1 and the sample A-2 are homopolymers, a single constituent unit in the composition of the polymer is completely continuously bonded, that is, the same type of monomer is not It consists of other types of early bodies and is continuously bonded. One-dimensional space (as a line segment of the comparison space Q) passing through two points of the coordinate point p (A-1) and the coordinate point P (A-2) is connected. Since the line segment (straight line) of the coordinate point P (A-1) and the coordinate point p (a-2) is arranged as a constituent unit, the same single body is continuously connected and arranged, so that the arrangement of the single unit is the highest in continuity. The evaluation distance L(S) from the line segment indicates the randomness of the arrangement of the monomers in the chain structure in the copolymer. For example, the numerical value conversion unit 313 specifies the numerical value a, the numerical value b, and the numerical value c as follows. a=PC2 (A-2) -PC2 (A-1) b = PCl (A-1) -PCI (A-2) c = -PC 1 ( A-1 ) x ( PC2 ( A-2 ) - PC2 (A-1 ) ) -PC2 ( A-1 ) x (PCI (A-1) -PCI (A-2)) 92 201222146 nuz.oopif 1 'Value a indicates the 2nd principal component The difference between the second principal component scores between the samples A 2 and 7 \ 2 on the PC 2. The value b indicates the ith principal component = the knife between the sample A-2 and the sample A-2 on the jffth axis PC1 The difference c. The value c is the result of multiplying the value a by the negative value of the result of the first main doubling knife of the sample A-1, and multiplying the value b by the second principal component of the sample A. The value of the negative value is added together.

、然後，數值轉換部313藉由以下的式進行計算而求出 通過樣品A-1與樣品A-2各自的座標點P (n)、座標點 P (A-2)這2點的比較空間Q的直線（一維空間）、與評 價對象的樣品S的座標點p (SPCl，SPC2)的評價距離L (S)此處，SPC1為樣品S的第1主成分得分，spc2為 第2主成分得分。 — L- | axSPCl+bxSPC2 + c | / (a2 + b2) 1/2 數值轉換部313如以上般算出評價距離L(s)。此處， 表示評價對象的聚合物的樣品S的點、與通過均聚物的樣 品A-1及樣品A-2的座標點p (a_i)及座標點p (八_2) 這2點的直線的評價距離L ( S )越大，共聚^鏈的無規性 越高。 即，本實施形態中的各主成分成為表示共聚合物中的 單體的排列的無規性的成分。其結果，可藉由評價距離L (S) ’而定性地評價共聚合物的鏈結構中的相同的單體的 連續配置的長度（同一種類的單體連續配置的數量）。 93 201222146. 其結果，自包含均聚物的座標點的空間的評價距離可 作為如下的基準，該基準可定性地判定同_種類的單體鄰 接地配置並處於嵌段化狀態的組成、與不随義單體鄰 接地配置的無規狀態的差別。 因此，特性評價部314作如下判定：評價對象的共聚 合物的樣品與包含均聚物的空間的評價距離L⑻越大， 共聚合物射的·單雜躺配㈣成的洲的無規性 越高。Then, the numerical value conversion unit 313 calculates the comparison space between the coordinate point P (n) and the coordinate point P (A-2) of each of the sample A-1 and the sample A-2 by the following equation. The straight line (one-dimensional space) of Q and the evaluation distance L (S) of the coordinate point p (SPCl, SPC2) of the sample S to be evaluated. Here, SPC1 is the first principal component score of the sample S, and spc2 is the second main component. Ingredient score. — L− | axSPCl+bxSPC2 + c | / (a2 + b2) The 1/2 numerical value conversion unit 313 calculates the evaluation distance L(s) as described above. Here, the point of the sample S of the polymer to be evaluated, the coordinate point p (a_i) of the sample A-1 and the sample A-2 which pass the homopolymer, and the coordinate point p (eight_2) are shown. The larger the evaluation distance L ( S ) of the straight line, the higher the randomness of the copolymerization chain. That is, each of the main components in the present embodiment is a random component indicating the arrangement of the monomers in the copolymer. As a result, the length of the continuous arrangement of the same monomers in the chain structure of the copolymer (the number of consecutively arranged monomers of the same kind) can be qualitatively evaluated by evaluating the distance L (S) '. 93 201222146. As a result, the evaluation distance from the space including the coordinate point of the homopolymer can be used as a criterion for qualitatively determining the composition of the monomer of the same type and being in a block state, and The difference in the random state in which the cells are not adjacently arranged. Therefore, the characteristic evaluation unit 314 determines that the evaluation distance L (8) of the sample of the copolymer to be evaluated and the space containing the homopolymer is larger, and the randomness of the continent is caused by the uniformity of the copolymer. The higher.

例如，特性評價部314亦能夠以如下方式構成：於内 部設定根據過去的實驗賴得的輯臨限值，當數值轉換 部313所算出的評價距離L⑻未滿所歧的距離臨限值 時，輸出表示作為抗姓劑用共聚合物不適合的恥信號， 另一方面，虽评價距離L (s)為距離臨限值以上時，輸出 表不適合於抗蝕劑用共聚合物的OK信號。 另外，特性評價部314亦能夠以如下方式構成：於内 部，據過去的實驗’針對評價輯L⑻於多個長度範圍For example, the characteristic evaluation unit 314 may be configured to internally set the margin value based on the past experiment, and when the evaluation distance L(8) calculated by the numerical value conversion unit 313 is less than the deviation threshold. The output indicates a shame signal which is not suitable as a copolymer for anti-surname. On the other hand, when the evaluation distance L (s) is equal to or greater than the distance threshold, the output table is not suitable for the OK signal of the resist copolymer. Further, the characteristic evaluation unit 314 can also be configured as follows: in the past, according to the past experiment 'for the evaluation series L(8) in a plurality of length ranges

1每一個内’表示包含溶解性及對於触感光度的微影製 私?性的數值’並根據所獲得的評價麟L(s)輸出使用 抓飯劑崎合物製備抗㈣用組成物時賴影製程 的數值。 ' 另外，利用上述無規性高的抗蝕劑用共聚合物 的抗簡组成物如後述的顧例所示般，顯影t = 劑的溶解性有魏提昇。糾，含有該共聚合物4= 用組成物於微歸程時㈣於柄感光度提昇。㈣ 94 201222146 wzoopif 作為可獲得該溶解性及對於光的感光度提昇的效果的 理由，可考慮以下的理由。 〜通常，共聚合物的合成中的各單體的使用量是對應於 欲獲得的單體組成的目標值而決定，且以使合成後的^聚 合物中的平均單體組成接近該目標的單體組成的方二宗 聚合條件等。 疋1In each of the 'representing the value of solubility and the lithography for the sensitivity of the touch sensitivity' and based on the obtained evaluation of the L (s) output using the rice cooker composition to prepare the anti-(4) composition The value of the shadow process. In addition, as shown in the following example, the anti-simplification composition of the copolymer for resist having high randomness is improved in the solubility of the developer t = agent. Correction, containing the copolymer 4 = when the composition is used in micro-return (4), the sensitivity of the handle is increased. (4) 94 201222146 wzoopif The following reasons can be considered as reasons for obtaining the solubility and the effect on the sensitivity of light. Usually, the amount of each monomer used in the synthesis of the copolymer is determined corresponding to the target value of the monomer composition to be obtained, and so that the average monomer composition in the synthesized polymer is close to the target. The polymerization conditions of the monomer composition are the same.疋

但疋，於多數情況下，進行共聚合的單體的共聚合反 應性比互不㈣’目此不無規地進行共聚合，所獲得的丑 聚合物的單體組成產生差異，並且於其絲合鏈ΐ的單^ 的配置中，形成同一種類的單體的嵌段而產生偏差。 的單體組成 尤其’於聚合反躺初減後期，單體組成 : 成含姆相同的構成單元“ 兀連接而成的聚合鏈會使對於溶劑的溶解❹化。籌成早 地二性;:工單元更均勻 :合物製備娜叫； 評價====::=: 201222146 用組成物， 物的特性。 而評價含有抗_用共聚合物的抗_用組成 即，於本實施形態中，提供如 劑用共聚合物時，藉㈣㈣減^万&amp;以價抗触 的細…L 士間地推_些共聚合物的鏈結構 可實際上不生成該抗㈣㈣組成物，進而實於 上不經過鄕製程步驟，而評價將 ==:；!微影製程特性’且可嚴格地評==:: 的曝光時的光的解析性、或顯影時的對於溶 的均一性 ' / 劑的溶解性 月&amp; 因此，本實施形態可容易地評價例如微影製程用 a物等共聚合物的鏈結射料體的配置的無規性，藉由 預先取得該無規性與使用料合物的域物的特性^關 聯’可進行所製備的組成物的評價，而並非如先前般，利 用共聚合物製備組餘，紐評制製備敝成物的特性。 另外，本實施形態因使用藉由NMR測定所獲得的 NMR光f#進行評價，故當如先前般推斷聚合物巾的單體的 定量或Μ分布時’林在由祕_溫度利起的試樣的 熱解效料不同、或無法定量地獲得反映構成單元的轨解 產物等測定誤.差，因此無需為了校正處理等而準備極=的 樣品數’可容易地進行組成物的評價。 [實例] 以下’藉由實例來具體地說明本發明，但本發明並不 限定於該些實例。 於以下的各例中，只要事先無特別說明，則表示為「份」However, in most cases, the copolymerization reactivity of the monomers subjected to copolymerization is not uniform (four)', and the monomer composition of the ugly polymer obtained is different, and In the arrangement of the filament strands, the blocks of the same type of monomers are formed to cause variations. The monomer composition is especially 'in the late stage of the initial reduction of the polymerization, the monomer composition: the same constituent unit of the same mer." The entangled polymer chain will decompose the solvent. Prepare the early sex; The unit is more uniform: the composition is prepared by the naming; evaluation ====::=: 201222146 The composition, the characteristics of the substance, and the composition of the anti-composition containing the anti-copolymer is evaluated, that is, in the present embodiment When a copolymer such as a solvent is provided, by (4) (4) minus ^ million &amp; valence resistance, the cross-linking of some of the copolymers may not actually form the anti-(four) (four) composition, and Without going through the 鄕 process step, the evaluation will be ==:;! lithography process characteristics' and the analyticity of the light at the time of exposure = or the uniformity of the solution at the time of development can be strictly evaluated' / In the present embodiment, it is possible to easily evaluate the irregularity of the arrangement of the link body of the copolymer such as a substance for the lithography process, and to obtain the randomness and use in advance. The characteristics of the domain of the composition can be evaluated by the composition of the prepared composition, not as prior In the past, the characteristics of the composition were prepared by the preparation of the copolymer, and the present embodiment was evaluated by using the NMR light f# obtained by NMR measurement, so that the polymer towel was inferred as before. When the quantification or enthalpy distribution of the monomer is different, the pyrolysis effect of the sample in the temperature-dependent sample is different, or the measurement of the misorientation of the orbital product reflecting the constituent unit is not quantitatively obtained, so there is no need to correct The composition can be easily evaluated by the number of samples prepared for the electrode or the like. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In the case of "No", unless otherwise stated

96 201222146 者是指「質量份」。樣品的分子量（重量平均分子量）、共 聚合物中的平均單體組成等的測定方法及評價方法使用以 下的方法。 (重罝平均分子量的測定） 共聚合物的重量平均分子量（Mw)及分子量分布 (Mw/Mn )是藉由 GPC ( Gel Permeation Chromatography， 凝膠滲透層析法），利用下述的GPC條件而以聚笨乙烯換 算來求出。 [GPC條件] 裝置：東曹（Tosoh)公司製造，東曹高速GPC裝置 HLC-8220GPC (商品名）， 分離管柱：昭和電工公司製造，串聯連結有3根Shodex GPCK-805L (商品名）者， 測定溫度：4〇°C， 溶離液：THF， 試樣（共聚合物的情況）：將約20 mg的共聚合物溶 解於5 mL的THF中，並利用0.5 μιη薄膜過濾器進行過濾 所得的溶液， 試樣（聚合反應溶液的情況）：將約30 mg的經採樣 的聚合反應溶液溶解於5 mL的THF中，並利用0.5 μιη薄 膜過據器進行過濾、所得的溶液， 流量：1 mL/分， 注入量：0.1 mL， 檢測器··示差折射計。 97 201222146 校準曲線I:使用將約20 mg的摞準聚笨乙烯溶解於5 mL的THF中，並以0.5 μιη薄膜過滤器進行過濾所得的溶 液’於上述條件下注入至分離管枉中’求出溶出時間與分 子量的關係。標準聚苯乙烯使用下述的東曹公司製造的標 準聚苯乙烯（均為商品名）。 F-80 (Mw = 706,000) &gt; F-20 (Mw= 190,000) &gt; F-4 (Mw = 37,900 )， F-l (Mw= 10,200) &gt; · A-2500 (Mw = 2,630) » A-500 ( Mw= 682、578、474、370、260 的混合物）。 (共聚合物的平均單體組成的測定） 將共聚合物的約5質量份溶解於氘化二甲基亞砜的約 95質量份中來製備試樣溶液。將該試樣溶液裝入至NMr 管中，使用iH-NMR (曰本電子（je〇L)公司製造，共振 頻率：270 MHz)進行分析。根據源自各構成單元的信號 的積分強度比而算出共聚合物的平均單體組成。 (單體的定量） · 殘存於聚合反應溶液中的單體量是藉由以下的方法而 求出。 提取反應器内的聚合反應溶液0 5g，利用乙腈對其進 行稀釋，然後使用定量瓶將總量設為5〇 。利用〇 2 的溥膜過遽器對該稀釋液進行過遽，然後使用東曹公司製 造的高速液相層析儀HPLC-8020 (製品名），針對每個單 98 201222146 wzoopif 體求出該稀釋液中的未反應單體量。 於《亥測疋中’以分離管柱使用1根Gl Sciences公司 製造的Inertsil〇DS-2 (商品名）、流動相為水/乙腈的梯度 系統、流量為0.8 mL/min、檢測器為東曹公司製造的紫外. 可見吸光光度計UV-8020(商品名）、檢測波長為220 nm、 測定溫度為40°C、注入量為4 pL來進行測定。再者，作 為分離管柱的Inertsil ODS-2 (商品名）使用矽膠粒徑5 μιη、管柱内徑4.6 mmx管柱長度450 mm者。另外，流動 相的梯度條件是將A液設為水’將B液設為乙腈，而如下 述般設定。另外，為了對未反應單體量進行定量，將濃度 不同的3種的各單體溶液用作標準液。 測定時間0分鐘〜3分鐘：A液/B液=90體積％八〇 體積％。 測定時間3分鐘〜24分鐘：A液/B液=自90體積％/1〇 體積％至50體積％/50體積％為止。 ’ 測定時間24分鐘〜36.5分鐘：A液/B液=自50體積 %/50體積％至0體積％/1〇〇體積％為止。 測定時間36.5分鐘〜44分鐘：A液/B液=0體積％/1〇〇 體積％。 (共聚合物的溶解性的評價） 利用下述的（1)或（2)的方法進行。 (1)將共聚合物 20 份與 PGMEA (Propylene Glycol Monomethyl Ether Acetate) 80份加以混合，一邊保持為 25°C—邊進行擾拌，以目視判斷完全溶解，並測定至完全 99 201222146 溶解為止的時間。 ⑵將聚合物2〇份與PGMEA80份加以混合， 25t —邊進行麟、，以目視_完全溶解後，添加 、元直至到達濁點為止，並败狀的添 的判斷是以目絲進行。 S mu (抗蝕劑組成物的感光度的評價） 將抗_域物旋轉塗佈於6，恃晶圓上，織於加 ^反上進行丨耽、6〇秒的預烤（PAB)，而形成厚度為 nm的抗歸。使用Arf7準好雷柯絲置⑴也。 Tech曰Japan&amp;司製造’製品名：π·韻〇)，一邊改變 、光^ —邊對l〇mmxl0mm的面積的18處進行曝光。繼 亍1KTC、6G秒的後烘烤（PEB)後，使用抗钮劑顯 衫/刀析,（Litho Tech Japan公司製造，製品名：RDA 8〇6 )， 下以2.38%氫氧化四甲基銨水溶液進行65秒顯 =。分別針對各曝光量的抗健，測定顯射的抗敍膜 的經時變化。 卞 基於所獲得的抗蝕膜厚的經時變化的資料，對曝光量 ^單位：mJ/cm2)的對數、與進行30秒顯影的時間點的殘 厚對於初始膜厚的比例率（單位，以下稱為殘膜 绫，=關係進行繪圖，製作曝光量-殘膜率曲線。根據該曲 ^(出用以使殘膜率為〇%的所需曝光量（Eth)的值。 不 [將曝光量-殘膜率曲線與殘膜率為0%的直線相交的點 曝光垔（mJ/cm2)作為Eth而求出。該Eth的值表 4、度，該值越小，表示感光度越高。 100 201222146 HU^OOpif 以下，對關於利用本實施形態的共聚合物評法 三單元組分率麟價的例進行賴。但是，本實施形態並 不限定於該些共聚合物的評價。 &lt;合成例A-1 :均聚物A-A-1 &gt; 於本合成例中，使下述單體（m-D單獨進行聚合。 [化3] …96 201222146 means “mass parts”. The following methods are used for the measurement method and evaluation method of the molecular weight (weight average molecular weight) of the sample, the average monomer composition in the copolymer, and the like. (Measurement of average molecular weight of heavy oxime) The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the copolymer are determined by GPC (Gel Permeation Chromatography) using the following GPC conditions. It is obtained by conversion of polystyrene. [GPC condition] Device: manufactured by Tosoh Corporation, HTC-8220GPC (trade name) of Tosoh Express Co., Ltd., Separation column: manufactured by Showa Denko Co., Ltd., connected with three Shodex GPCK-805L (trade name) in series , Determination of temperature: 4 ° ° C, Solvent: THF, sample (in the case of co-polymer): about 20 mg of the copolymer was dissolved in 5 mL of THF, and filtered using a 0.5 μm membrane filter Solution, sample (in the case of polymerization solution): About 30 mg of the sampled polymerization solution was dissolved in 5 mL of THF, and filtered using a 0.5 μm thin film filter, the resulting solution, flow rate: 1 mL/min, injection volume: 0.1 mL, detector··differential refractometer. 97 201222146 Calibration curve I: A solution obtained by dissolving about 20 mg of ruthenium polystyrene in 5 mL of THF and filtering with a 0.5 μm membrane filter was injected into the separation tube under the above conditions. The relationship between the dissolution time and the molecular weight. Standard polystyrene uses the following standard polystyrene (both trade names) manufactured by Tosoh Corporation. F-80 (Mw = 706,000) &gt; F-20 (Mw= 190,000) &gt; F-4 (Mw = 37,900), Fl (Mw= 10,200) &gt; · A-2500 (Mw = 2,630) » A-500 (Mw = a mixture of 682, 578, 474, 370, 260). (Measurement of Average Monomer Composition of Copolymer) A sample solution was prepared by dissolving about 5 parts by mass of the copolymer in about 95 parts by mass of deuterated dimethyl sulfoxide. The sample solution was placed in a NMr tube and analyzed by iH-NMR (manufactured by Sigma Electronics Co., Ltd., resonance frequency: 270 MHz). The average monomer composition of the copolymer was calculated from the integrated intensity ratio of the signals derived from the respective constituent units. (Quantification of Monomer) The amount of the monomer remaining in the polymerization reaction solution was determined by the following method. The polymerization solution in the reactor was extracted from 0 5 g, diluted with acetonitrile, and then the total amount was set to 5 Torr using a metering bottle. The dilution was subjected to enthalpy using a 〇2 溥 membrane filter, and then the dilution was determined for each single 98 201222146 wzoopif body using a high-speed liquid chromatography HPLC-8020 (product name) manufactured by Tosoh Corporation. The amount of unreacted monomer in the liquid. In the "Self Test", one Seltsil® DS-2 (trade name) manufactured by Gl Sciences, a gradient system of mobile phase water/acetonitrile, a flow rate of 0.8 mL/min, and a detector were used. The UV-visible spectrophotometer UV-8020 (trade name) manufactured by Cao Company, the detection wavelength was 220 nm, the measurement temperature was 40 ° C, and the injection amount was 4 pL. Further, Inertsil ODS-2 (trade name) used as a separation column used a silica gel particle size of 5 μm, a column inner diameter of 4.6 mmx, and a column length of 450 mm. Further, the gradient condition of the mobile phase was such that the liquid A was made into water' and the liquid B was made into acetonitrile, and it was set as follows. Further, in order to quantify the amount of unreacted monomers, three kinds of monomer solutions having different concentrations were used as standard solutions. Measurement time: 0 minutes to 3 minutes: Liquid A/B solution = 90% by volume of octa vol%. The measurement time is 3 minutes to 24 minutes: A liquid / B liquid = from 90% by volume / 1% by volume to 50% by volume / 50% by volume. 'Measurement time 24 minutes to 36.5 minutes: A liquid / B liquid = from 50% by volume / 50% by volume to 0% by volume / 1% by volume. The measurement time was 36.5 minutes to 44 minutes: A liquid / B liquid = 0% by volume / 1% by volume. (Evaluation of Solubility of Copolymer) The method of (1) or (2) below was carried out. (1) 20 parts of the copolymer and 60 parts of PGMEA (Propylene Glycol Monomethyl Ether Acetate) were mixed and spoiled while maintaining the temperature at 25 ° C, and it was visually judged to be completely dissolved, and measured until completely 99 201222146 was dissolved. time. (2) Two parts of the polymer were mixed with 80 parts of PGMEA, and 25t was used to carry out the lining, and after visually _ completely dissolved, the element was added until the cloud point was reached, and the judgment of the addition was judged by the eye. S mu (Evaluation of Sensitivity of Resist Composition) The anti-domain material was spin-coated on 6, and the wafer was woven, and the ruthenium was pre-baked (PAB) for 6 sec. And the formation of a thickness of nm anti-return. Use Arf7 to get the ray (1) also. Tech 曰 Japan &amp; Division made 'product name: π · rhyme ,), while changing, light ^ - exposed 18 areas of l 〇 mmxl0mm area. After 1KTC and 6G seconds of post-baking (PEB), use the anti-button agent to form a shirt/knife, (Litho Tech Japan, product name: RDA 8〇6), with 2.38% tetramethylammonium hydroxide The aqueous ammonium solution was subjected to 65 seconds. The temporal change of the marked anti-suppressed film was measured for each of the exposure resistances.卞Based on the obtained time-dependent change in the thickness of the resist film, the logarithm of the exposure amount unit: mJ/cm 2 ), and the ratio of the residual thickness at the time point at which the development was performed for 30 seconds to the initial film thickness (unit, Hereinafter, the residual film 绫, = relationship is plotted, and the exposure amount-residual film rate curve is produced. According to the curve, the value of the required exposure amount (Eth) for making the residual film rate 〇% is not [will The exposure amount-residual film rate curve and the point exposure 垔(mJ/cm2) at which the residual film rate is 0% intersect with each other as the Eth. The value of the Eth is shown in Table 4 and the degree. The smaller the value, the higher the sensitivity. 100 201222146 HU^OOpif The following is an example of the use of the copolymer evaluation triblock component rate of the present embodiment. However, the present embodiment is not limited to the evaluation of these copolymers. &lt;Synthesis Example A-1: Homopolymer AA-1 &gt; In the present synthesis example, the following monomers (mD were separately polymerized. [Chemical 3] ...

(m— 1) 首先，將5.00份的單體（m-1 )、2.03份的二曱基_2 2，-偶氮雙異丁酸酯（和光純藥工業公司製造，V60l(商品名）） 與11.7份的乳酸乙醋一同添加至25 mL的舒倫克燒瓶 (Schlenk flask )中，然後以200 mL/分向溶液内吹入氮氣 1分鐘。繼而，將該燒瓶置於80°C的水浴上，一邊授掉一 邊攪拌3小時。 繼而，一邊授拌一邊將所獲得的反應溶液滴加至約2〇 倍量的曱醇中，獲得白色的析出物（均聚物A-A_l)的沈 澱。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。於 減壓下以40°C對該共聚合物濕粉進行約40小時乾燥，獲 得白色粉體（4.45 g)。 &lt;合成例A-2〜合成例A-5 :均聚物A-A-2〜均聚物 101 201222146 ~Γ、/X1 A-A-5 &gt; 製造下述單體（m-2)〜單體（m-5)各自的單獨單體。 即，除如表1所示般變更所使用的單體及其量以外，以與 合成例A-1相同的操作，獲得均聚物A-A-2〜均聚物 A-A-5。將所獲得的均聚物A-A-1〜均聚物A-A-5的加入 組成（加入單體組成比）、產率示於表1。 [化4](m-1) First, 5.00 parts of monomer (m-1), 2.03 parts of dimercapto-2 2,-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., V60l (trade name) It was added to a 25 mL Schlenk flask together with 11.7 parts of ethyl lactate, and then nitrogen gas was blown into the solution at 200 mL/min for 1 minute. Then, the flask was placed on a water bath at 80 ° C, and stirred while being allowed to stand for 3 hours. Then, the obtained reaction solution was added dropwise to about 2 Torr of decyl alcohol while stirring, to obtain a precipitate of a white precipitate (homopolymer A-A-1). Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer wet powder was dried at 40 ° C under reduced pressure for about 40 hours to obtain a white powder (4.45 g). &lt;Synthesis Example A-2 to Synthesis Example A-5: Homopolymer AA-2 to Homopolymer 101 201222146 ~Γ, /X1 AA-5 &gt; The following monomers (m-2) to monomers were produced ( M-5) respective individual monomers. Specifically, a homopolymer A-A-2 to a homopolymer A-A-5 were obtained in the same manner as in the synthesis example A-1 except that the monomers used and the amounts thereof were changed as shown in Table 1. The composition of the obtained homopolymer A-A-1 to homopolymer A-A-5 (addition of monomer composition ratio) and the yield are shown in Table 1. [Chemical 4]

(m— 2) (m — 3) (m—4) (m— 5) [表l] 聚合 物 加入單體質量/g 加入單| 豊組成比/mol% 產率/% m-1 m-2 ni'3 m-4 m-5 m-1 m-2 m-3 m-4 m-5 A-A-1 5.00 100 89.1 A-A-2 5.00 100 78.6 A-A-3 5.00 100 68.8 A-A-4 5.00 100 91.2 A-A-5 5.00 100 74.3(m-2) (m-3) (m-4) (m-5) [Table l] Polymer addition monomer mass / g Addition mono | 豊 composition ratio / mol% Yield /% m-1 m- 2 ni'3 m-4 m-5 m-1 m-2 m-3 m-4 m-5 AA-1 5.00 100 89.1 AA-2 5.00 100 78.6 AA-3 5.00 100 68.8 AA-4 5.00 100 91.2 AA -5 5.00 100 74.3

&lt;合成例A-6 :二元共聚合物A-B-l&gt; 於本合成例中，使單體（m-1 )、單體（m-2)進行共 聚合。 事先將所有單體及溶劑加入至燒瓶内，以批量方式合 成共聚合物。本例中所使用的單體的莫耳比為（m-Ι): 102 201222146 -rv/ζ,οοριΐ (m-2) = 10.0 : 90.0 〇 即，將乳酸乙酯13.5份、單體（m-1) 0.51份、單體 (m-2) 5.29份、單體（m-3) 0.51份、二曱基-2,2，-偶氮雙 異丁酸酯（上述的V601 (商品名））0.57份加入至25 mL 的舒倫克燒瓶中後，以200 mL/分向溶液内吹入氮氣1分 鐘。繼而’將該燒瓶置於8〇。(：的水浴上，攪拌後，於3分 鐘後利用冰水急速冷卻反應溶液。 繼而’ 一邊攪拌一邊將所獲得的反應溶液滴加至約1〇 倍量的甲醇/水= 50/50 (容量比）中，獲得白色的析出物 (共聚合物A-B-1)的沈澱。然後，將清洗後的沈澱濾除， 獲得共聚合物濕粉。於減壓下以4〇°c對該共聚合物濕粉進 行約40小時乾燥’獲得白色粉體（〇 232 g)。 所獲得的共聚合物的平均單體組成（以下，有時亦記 作共聚合組成）為（md) / (m_2) = 15 5/84 5 (莫耳％)。 〈合成例A-7〜合成例α·32&gt; 除如表2、表3所示般變更所使用的單體的量以外， • W與合成例Α_6相同的操作，獲得共聚合物Α_Β-2〜共聚 合物A_B_27。將所獲得的共聚合物〜共聚ς物 Α-Β-27的產率、共聚合組成示於表2、表3。 而且，關於合成例Α_6〜合成例Α_1()，㈣加人㈣ 比與共聚合物Α·Β_1〜絲合物A_B_5的共聚合組成，並 藉由曲線々合法所求出的單體㈤）及單體（m_2)的丘 聚合反應性比分別成為Γ12：=1 484、γ21 = 〇如。以相同方 式’根據共聚合物α_β_6〜共聚合物Α Β·27的共聚合組成 103 201222146 而求出各共聚合反應性比，並將其示於表4。表4中表示 共聚合物A-B-1〜共聚合物A-B-27的共聚合組成與各共聚 合反應性比的對應。 &lt;合成例A-33 :三元共聚合物A-C-1〉 於本合成例中，使單體（m-1)、單體（m-2)、單體（m_3) 進行共聚合。 事先將所有單體及溶劑加入至燒瓶内，以批量方式合 成共聚合物。本例中所使用的單體的莫耳比為：心丨）： (m-2) : (m_3) =30.0 : 30.0 : 40.0 ° 即’將乳酸乙g旨14.3份、單體（m-1) 1.53份、單體 (m-2) 1.76份、單體（m-3) 2.83份、二曱基_2,2，-偶氮雙 異丁酸酯（上述的V601 (商品名））1.41份加入至25 mL 的舒倫克燒瓶中後，以200 mL/分向溶液内吹入氮氣1分 鐘。繼而，將該燒瓶置於80°C的水浴上，攪拌後，於3分 鐘後利用冰水急速冷卻反應溶液。 繼而，一邊攪拌一邊將所獲得的反應溶液滴加至約10 倍量的曱醇/水= 50/50 (容量比）中，獲得白色的析出物 (共聚合物A-C-1)的沈澱。 然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。於 減壓下以40°C對該共聚合物濕粉進行約40小時乾燥，獲 得白色粉體（0.276 g)。 &lt;合成例A-34〜合成例A-42&gt; 除如表5、表6所示般變更所使用的單體及其量以外， 以與合成例A-33的操作，獲得共聚合物A-C-2〜共聚合物 201222146 4UZ58plf A_C-10。將所獲得的共聚合物 的產率、共聚合組成示於表5、表6_。〜、聚合物A-C_1〇 以下的例A-D卜例A-D3是藓由料旦1 製造方法的實施形態⑵，）的= = 程用聚合物的 物的例，例A_D2、例A-D4是葬:取::來製造共聚合 滴加方式來製造共聚合物的例^二2(Z1)的部分 ::::一共聚合物求咖單 〈例A-D1 :共聚合物八七1 &gt; [共聚合物的製造] 於本例中’藉由部分滴加 (叫、單體（m-3)進行聚合。早溫㈤）、早體 =用2種含有單體的滴加溶液，於 滴力:溶液後’滴加另-方的滴力丄』 DO ，滴加/谷液是如下的滴加溶液：上述3種單體之中， 早體消耗速度最快的單體的組成比大於聚合反應中所使用 斤有;谷液的總罝中的該皁體的組成比，且不含覃辦、、奋餐 迷度最慢的單體。 / 本例中所使用的各單體的合計量的莫耳比為（m_i): ^-2) : (m-3) =39.1 : 41.2 ： 19.7 〇 於氮氣環境下，將乳酸乙酯99.3份、單體】3 早體m-2 7.68份、單體m-3 2.88份加入至具備氮氣導 105 201222146 、滴液漏斗、及溫度計的燒瓶中。 一邊對燒瓶内進行授拌一邊將水浴 入口、授掉機、冷凝5| 將燒瓶放入至水浴中， 的溫度提南至。 其後，自加入有乳酸乙酯2.0份與二曱基_2,2，·偶氮雙 異丁 Wa (上述的V6G1 (商品名））丨份的滴加褒置， ㈣定速度歷時20分鐘向燒瓶内進行滴加，並且自加入有 單體m-1 24.03份、單體m_2 27/71份、單體心3 16 68份、 礼酸乙酯1G1.8份、二甲基_2,2，_偶氮雙異丁酸(上述的 V601 (商品名））〇·_份的滴加裝置，以固定速度歷時* 小時向燒瓶内進行滴加。繼而，歷時丨小時滴加含有單體 m-1 1.09份、單體m_3 0.73份、乳酸乙酯34.5份、二甲基 -2,2’-偶氮雙異丁酸酯（上述的V6〇1 (商品名））〇 〇54份 的浴液中的80質量％後’歷時1小時滴加2〇質量％。 進而，於滴加結束後將80°C的溫度保持1小時。 繼而，一邊攪拌一邊將燒瓶内的聚合反應溶液滴加至 約10倍量的曱醇及水的混合溶劑（曱醇/水= 80/20容量比） 中’獲得白色的析出物（共聚合物A-D-1)的沈殿。將沈 澱濾除’再次投入至與上述相同量的曱醇及水的混合溶劑 (甲醇/水= 90/10容量比）中，一邊攪拌一邊進行沈澱的 清洗。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。 於減壓下以40°C對該共聚合物濕粉進行約40小時乾燥， 獲得白色粉體（69.9 g)。 然後，利用W-NMR與GPC對所獲得的白色粉體進 行分析，並求出共聚合物整體的平均單體組成、分子量 106 201222146 H-uzoopif&lt;Synthesis Example A-6: Binary copolymer A-B-1&gt; In the present synthesis example, the monomer (m-1) and the monomer (m-2) were copolymerized. All of the monomers and solvent were added to the flask in advance to form a copolymer in a batch manner. The molar ratio of the monomer used in this example is (m-Ι): 102 201222146 -rv/ζ, οοριΐ (m-2) = 10.0 : 90.0 〇, ie, ethyl lactate 13.5 parts, monomer (m -1) 0.51 part, monomer (m-2) 5.29 part, monomer (m-3) 0.51 part, dimercapto-2,2,-azobisisobutyrate (V601 (trade name) mentioned above) After adding 0.57 parts to a 25 mL Schlenk flask, nitrogen gas was blown into the solution at 200 mL/min for 1 minute. Then the flask was placed at 8 Torr. On the water bath of (:, after stirring, the reaction solution was rapidly cooled with ice water after 3 minutes. Then, the obtained reaction solution was added dropwise to about 1 Torr of methanol/water = 50/50 while stirring. In the ratio, a precipitate of white precipitate (copolymer AB-1) was obtained. Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymerization was carried out at 4 ° C under reduced pressure. The wet powder was dried for about 40 hours to obtain a white powder (〇232 g). The average monomer composition of the obtained copolymer (hereinafter, sometimes also referred to as copolymerization composition) was (md) / (m_2) = 15 5/84 5 (mol%). <Synthesis Example A-7 to Synthesis Example α·32> In addition to the amount of the monomer used as shown in Table 2 and Table 3, • W and the synthesis example The same operation of Α_6 gave the copolymer Α_Β-2 to the copolymer A_B_27. The yield and copolymerization composition of the obtained copolymer ~ copolymer Α-Β-27 are shown in Table 2 and Table 3. , for the synthesis example Α_6~synthesis example Α_1(), (d) plus (4) the copolymerization composition with the copolymer Α·Β_1~filament A_B_5, and by means of The ratio of the monomeric reactivity of the monomer (5)) and the monomer (m_2) determined by the enthalpy is Γ12:=1 484, γ21 = 〇. The copolymerization reactivity ratio was determined in the same manner from the copolymerization composition 103 201222146 of the copolymer α_β_6 to the copolymer Α·27, and is shown in Table 4. Table 4 shows the correspondence between the copolymerization composition of the copolymer A-B-1 to the copolymer A-B-27 and the reactivity ratio of each copolymerization. &lt;Synthesis Example A-33: Ternary Copolymer A-C-1> In the present synthesis example, the monomer (m-1), the monomer (m-2), and the monomer (m_3) were copolymerized. All of the monomers and solvent were added to the flask in advance to form a copolymer in a batch manner. The molar ratio of the monomer used in this example is: palpitations: (m-2) : (m_3) = 30.0 : 30.0 : 40.0 ° That is, 'will make 14.3 parts of lactate, monomer (m-1) 1.53 parts, monomer (m-2) 1.76 parts, monomer (m-3) 2.83 parts, dimercapto-2,2,-azobisisobutyrate (V601 (trade name) above) 1.41 After adding a portion to a 25 mL Schlenk flask, nitrogen gas was blown into the solution at 200 mL/min for 1 minute. Then, the flask was placed in a water bath at 80 ° C, and after stirring, the reaction solution was rapidly cooled with ice water after 3 minutes. Then, the obtained reaction solution was added dropwise to about 10 times the amount of decyl alcohol/water = 50/50 (capacity ratio) while stirring to obtain a precipitate of a white precipitate (copolymer A-C-1). Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer wet powder was dried at 40 ° C under reduced pressure for about 40 hours to obtain a white powder (0.276 g). &lt;Synthesis Example A-34 to Synthesis Example A-42&gt; In addition to the monomers and amounts thereof used as shown in Tables 5 and 6, the copolymer AC was obtained by the operation of Synthesis Example A-33. -2~copolymer 201222146 4UZ58plf A_C-10. The yield and copolymerization composition of the obtained copolymer are shown in Table 5 and Table 6_. ~, polymer A-C_1〇 The following examples of the example of AD, A-D3, are examples of the embodiment of the method (2), of the production method of the production method, and the example of the polymer of the process, the example A_D2, the example A-D4 It is a funeral: Take: to make a copolymerization method to make a copolymer of the example ^ 2 2 (Z1) part:::: a total polymer request for a coffee list <Example A-D1: Copolymer 787 &gt; [Manufacture of co-polymer] In this example, 'by partial addition (called, monomer (m-3) polymerization. Early temperature (five)), early body = two kinds of monomer-containing dropping solution In the drop force: after the solution, 'drop the other side of the drop force 丄』 DO, drop / gluten is the following drop solution: among the above three kinds of monomers, the fastest consumption of the monomer in the early body The composition ratio is greater than the amount of the soap used in the polymerization reaction; the composition ratio of the soap body in the total mash of the gluten solution, and does not contain the monomer which is the slowest and the slowest. / The molar ratio of the total amount of each monomer used in this example is (m_i): ^-2) : (m-3) = 39.1 : 41.2 : 19.7 99.3 parts of ethyl lactate under nitrogen atmosphere , monomer] 3 early body m-2 7.68 parts, monomer m-3 2.88 parts were added to a flask equipped with a nitrogen gas guide 105 201222146, a dropping funnel, and a thermometer. While the inside of the flask was being stirred, the water bath was introduced, the machine was allowed to be condensed, and the flask was placed in a water bath, and the temperature was raised to the south. Thereafter, a dropping device of 2.0 parts of ethyl lactate and dimercapto-2,2,-azobisisobutyl Wa (the above-mentioned V6G1 (trade name)) was added, and (4) a constant speed of 20 minutes was added. The inside of the flask was added dropwise, and 24.01 parts of the monomer m-1, 27/71 parts of the monomer m_2, 3 16 68 parts of the monomer core, 1.8 parts of the ethyl oxalate, and dimethyl 2 were added. 2,_Azobisisobutyric acid (V601 (trade name) above) 〇·_ part of the dropping device was dropped into the flask at a fixed speed for 4 hours. Then, 1.09 parts of the monomer m-1, 0.73 parts of the monomer m_3, 34.5 parts of ethyl lactate, and dimethyl-2,2'-azobisisobutyrate (V6〇1 described above) were added dropwise over several hours. (trade name)) After 80% by mass of the bath solution of 54 parts, 2% by mass was added dropwise over 1 hour. Further, after the completion of the dropwise addition, the temperature at 80 ° C was maintained for 1 hour. Then, the polymerization reaction solution in the flask was dropwise added to a mixed solvent of decyl alcohol and water (sterol/water = 80/20 capacity ratio) while stirring to obtain white precipitates (copolymer) The hall of AD-1). The precipitate was filtered off and returned to the mixed solvent (methanol/water = 90/10 volume ratio) of the same amount of decyl alcohol and water as described above, and the precipitate was washed while stirring. Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer wet powder was dried at 40 ° C under reduced pressure for about 40 hours to obtain a white powder (69.9 g). Then, the obtained white powder was analyzed by W-NMR and GPC, and the average monomer composition and molecular weight of the entire copolymer were determined. 106 201222146 H-uzoopif

Mw及分子量分布（Mw/Mn)i外，利用上述方法 所獲知的共聚合物Α·ϋ·1的溶解性。將其結果示於表7。只 將共聚合物Α-D-l〜共聚合物A_D_4、及共聚合物 A-E_l〜共聚合物A_E_4各自的組成中的單體瓜」〜單 的共聚合組成比、分子量（Mw )、分子量分 (Mw/Mn)、作為評價值的單體三單元組分率的預测值、 ，。示溶解__ (分鐘）、作為感光度的曝光量示於該表 [抗姓劑組成物的製造] 於上述所獲得的共聚合物A D1的1〇〇份中混合 二酸產生劑的三苯基錡三氟曱細酸鹽2份、及作為密 的PGMEA 700份來製成均勻溶液後，利用孔徑為^ 1 的薄膜過濾器進行過濾，而製$ ] μηι 該所獲得的抗_組成物，= 。針對 其結果示於表7。 Κ方法_感光度。將 〈例A-D2 ·共聚合物a_d_2&gt; 於本例中，藉由部分滴加 (叫、單體㈤）進行聚^早㈤）、單體 單體液'僅使用含有單體㈣' 本例中所滴加溶液。 )=39.0早4=7*的莫耳比為(--〇: 於氮氣環境下，將乳酸乙 De 份、單體㈤)4.9。份、單乙二79.=二體(-1 ) 2刀 早體（m-3) 2.02份加入至與例 107 201222146The solubility of the copolymer Α·ϋ·1 obtained by the above method, in addition to Mw and molecular weight distribution (Mw/Mn) i. The results are shown in Table 7. Only the copolymerization ratio, molecular weight (Mw), and molecular weight of the monomeric melons in the composition of the copolymers Α-D1 to the copolymer A_D_4 and the copolymers A-E-1 to the copolymer A_E_4 (Mw/Mn), a predicted value of the monomer triad fraction as an evaluation value, . Dissolution __ (minutes), exposure amount as sensitivity is shown in the table [manufacture of anti-surname composition] Three of diacid generators are mixed in one part of the above-obtained copolymer A D1 2 parts of phenyl fluorene trifluoromethane fine salt and 700 parts of dense PGMEA to form a homogeneous solution, and then filtered with a membrane filter having a pore diameter of ^ 1 to prepare an anti-component composed of $ ] μηι Object, = . The results are shown in Table 7. Κ Method _ sensitivity. <Example A-D2 ·Copolymer a_d_2> In this example, by partial addition (called, monomer (5)), poly (early (f)), monomer monomer liquid 'only contains monomer (four)' The solution was added dropwise in the example. ) = 39.0 early 4 = 7 * molar ratio is (-- 〇: under nitrogen atmosphere, lactic acid B parts, monomer (f)) 4.9. Parts, single E 2 79. = two bodies (-1) 2 knives Early body (m-3) 2.02 parts added to the example 107 201222146

i \J ΛιΛ \J A-Dl相同的燒瓶中。將燒瓶放入至 進行攪拌’-邊使水關溫度上昇至⑽。c ’。-邊對繞瓶内 其後，自加入有乳酸乙醋3.6份與。 異丁酸酯（上述的V601 (商品名））鸽氮雙 _定速度歷時15分鐘向燒瓶内裝置， 单體㈤m80份、單體(m_2) 2744份、單&amp;入有 16.52份、乳酸乙酯98.06份、二曱基_2 2 m_3)i \J ΛιΛ \J A-Dl in the same flask. The flask was placed until stirring, and the water-off temperature was raised to (10). c ’. - Between the bottles and the inside of the bottle, 3.6 parts of lactic acid ethyl acetate were added. Isobutyrate (V601 (trade name) above) pigeon nitrogen double-fixed speed for 15 minutes into the flask, monomer (f) m80 parts, monomer (m_2) 2744 parts, single &amp; with 16.52 parts, lactate B 98.06 parts ester, dimercapto 2 2 m_3)

(上述的糊（商品名））論3份的滴加/置，以^= 度歷時4小時向燒瓶内進行滴加。進而 执 為80°C並將燒瓶保持3小時。 ^後’以與例A-m相同的方式獲得白色的析出物（共 的沈殿’進行滤除、清洗、清洗後的滤除、 乾餘而獲得白色粉體（66.0g)。 —對所獲得的共聚合物A-D-2進行與例A_D1相同的測 定及評價。將其結果示於表7。 &lt;例A-E1 :共聚合物A-E-1 &gt;(The above-mentioned paste (trade name)) 3 drops were added/dropped, and the inside of the flask was dropped by ^= for 4 hours. Further, the temperature was maintained at 80 ° C and the flask was kept for 3 hours. After the white precipitates were obtained in the same manner as in Example Am (the total of the slabs were filtered, washed, washed, filtered, and dried to obtain a white powder (66.0 g). The polymer AD-2 was subjected to the same measurement and evaluation as in Example A_D1. The results are shown in Table 7. <Example A-E1: Copolymer AE-1 &gt;

於例A-D1中，事先不將單體加入至燒瓶~，而藉由 整體滴加方式來合成共聚合物。本例中所使用的單體的莫 耳比為（m-1 ) : ( m-2 ) : ( m-3 )= 40.0 : 40.0 : 20.0。 尸’於氛氣％丨兄下，將乳酸乙g旨64.5份加入至與例 A-D1相同的燒瓶中。將燒瓶放入至水浴中，一邊對燒瓶内 進行攪拌一邊使水浴的溫度上昇至80°C。 其後，自加入有單體（m-1 ) 27.20份、單體（m_2) 31.36份、單體（m_3；) 18 88份、乳酸乙酯112 6份、二甲 108 201222146 WZ5〇pif ί二=異述的V6。1 (商品名))2.576 聚合，的方式獲得白色的析出物(共 乾燥而散繼的據除、In Example A-D1, the monomer was not added to the flask beforehand, and the copolymer was synthesized by the integral dropping method. The molar ratio of the monomer used in this example was (m-1) : ( m-2 ) : ( m-3 ) = 40.0 : 40.0 : 20.0. The corpse was added to the same flask as in Example A-D1 under the atmosphere of 5%. The flask was placed in a water bath, and the temperature of the water bath was raised to 80 ° C while stirring the inside of the flask. Thereafter, 27.20 parts of the monomer (m-1), 31.36 parts of the monomer (m_2), 1888 parts of the monomer (m_3;), 112 6 parts of ethyl lactate, and dimethyl 108 201222146 WZ5〇pif ί are added. = V6.1 (trade name) of the dissident) 2.576 Polymerization, the method of obtaining white precipitates (co-drying and scattering)

定及::;獲===-:進行與例a-di相同的測 例Α·Ε2 .共聚合物α_ε·2&gt; 並夢mi_D1、巾，事先將所有單體及溶劑加人至燒瓶内， 莫‘比方式來合成共聚合物。本例中所使用的單體的 、 办1)“111·2)、11^) =40.0:40.0: 20 0。 ^將乳酸乙酯15·5份、單體（W) ^ 36份、 異;酸二份、單體㈤)〇.94份、二曱基心，偶氮雙 異丁酉鳴（上述的V601 (商品名））U5份加入至25扯 的舒偷克燒瓶中後，以200 mL/分向溶液内吹入氮氣1分 鐘。繼而，將該燒瓶置於80°C的水浴上，一邊攪拌一邊 拌3小時。 i 繼而’ 一邊攪拌一邊將所獲得的反應溶液滴加至約1〇 倍量的甲醇中’獲得白色的析出物（共聚合物A-E-2)的 沈澱。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。 於減壓下以40°C對該共聚合物濕粉進行約4〇小時乾燥， 獲得白色粉體（2·8 g)。 對所獲得的共聚合物A-E-2進行與例A-D1相同的測 109 201222146 定及評價。將其結果示於表7。 〈例A-D3 :共聚合物A-D-3〉 [共聚合物的製造] 於本例中，藉由部分滴加方式來使單體（m-4)'舉體 (m-5)、單體（m-3)進行聚合。作為含有單體的滴加溶 液，使用與例A-D1相同的2種滴加溶液。 本例中所使用的各單體的合計量的莫耳比為（m_4): (m_5) : (m-3) =39.1 : 41.2 : 19.7。And ===-: The same test as the example a-di Α·Ε2. Copolymer α_ε·2&gt; and dream mi_D1, towel, all the monomers and solvent were added to the flask in advance , Mo's way to synthesize copolymers. In the case of the monomer used in this example, 1) "111·2), 11^) = 40.0: 40.0: 20 0. ^ 1.5 parts of ethyl lactate, monomer (W) ^ 36 parts, different 2 parts of acid, monomer (5)) 〇.94 parts, diterpene base, azobisisobutyl hydrazine (V601 (trade name) above) U5 parts were added to the 25-stripped Shutike flask, to 200 Nitrogen gas was blown into the solution for 1 minute. Then, the flask was placed in a water bath at 80 ° C, and stirred for 3 hours while stirring. i Then 'the reaction solution obtained was added dropwise to about 1 while stirring. Precipitation of white precipitates (copolymer AE-2) was obtained in a helium-dosing amount of methanol. Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The pressure was reduced at 40 ° C under reduced pressure. The copolymer wet powder was dried for about 4 hours to obtain a white powder (2·8 g). The obtained copolymer AE-2 was subjected to the same measurement as in Example A-D1, 109 201222146, and evaluated. The results are shown in Table 7. <Examples A to D3: Copolymer AD-3> [Production of Copolymer] In this example, the monomer (m-4) was lifted by a partial dropping method ( M-5), monomer (m-3) As the dropping solution containing the monomer, the same two kinds of dropping solutions as in the examples A-D1 were used. The molar ratio of the total amount of each monomer used in this example was (m_4): (m_5): (m-3) = 39.1 : 41.2 : 19.7.

於氮氣環境下，將乳酸乙g旨46.5份、PGMEA 46.5份 單體m-4 2.60份、單體m_5 10.13份、單體m_3 3 3〇二 入至具備氮氣導入口、攪拌機、冷凝器、滴液漏斗、及、 度計的燒瓶中。將燒瓶放人至水財，—邊對燒瓶内進= 攪拌一邊將水浴的溫度提高至746.5 parts of lactic acid, 46.5 parts of PGMEA 46.5 parts, 10.13 parts of monomer m_5, and monomer m_3 3 3 were placed in a nitrogen atmosphere to have a nitrogen inlet, a stirrer, a condenser, and a drop. In the funnel, and in the flask of the meter. Put the flask to the water, and increase the temperature of the water bath to 7 while stirring in the flask.

其後，自加入有乳酸乙酯6.5份與 雙異丁酸醋（上述的V601 (商品名）） ，偶A 置，以固定速度歷時2。分鐘向燒瓶内進行:、力口裝 與該滴加處理的同時，自加入有單體 6 口 °另外，Thereafter, 6.5 parts of ethyl lactate and bis-isobutyric acid vinegar (V601 (trade name) as described above) were added, and even A was placed at a fixed rate for 2 hours. Minutes are carried out in the flask:, at the same time as the dropwise addition treatment, the monomer 6 is added at the same time.

m-5 24.30份、單體㈤24 〇〇份 =6伤、單體 顺EA 33·4份、二甲基-2,2，-偶氮雙恩丁^⑽份、 V6〇1 (商品名））1賴份的滴加裝置乂=上述的 4小時向燒瓶内進行滴加。 u疋速度歷時 繼而，歷時1小時滴加含有單體m m-3 U2份 '乳酸乙黯12 2份、腦 '單體M-5 24.30 parts, monomer (5) 24 parts = 6 wounds, monomer cis EA 33·4 parts, dimethyl-2,2,-azobisdine (10) parts, V6〇1 (trade name) 1) A dropping device 乂 = the above-mentioned 4 hours was dropped into the flask. u疋Speed duration Then, the monomer m m-3 U2 part was added dropwise for 1 hour, '2 parts of lactate, 2 'brain'

处偶_丁_ (上述的蘭（商品名2)，gH 110 201222146 ^tuzoepif 的溶液中的80質量％後，歷時1小時滴加2〇質量％。進 而，將80°C的溫度保持1小時。In the above-mentioned blue (trade name 2), 80% by mass in the solution of gH 110 201222146 ^tuzoepif, 2% by mass was added dropwise over 1 hour. Further, the temperature at 80 ° C was maintained for 1 hour. .

繼而’一邊攪拌一邊將燒瓶内的聚合反應溶液滴加至 約10倍量的曱醇及水的混合溶劑（曱醇/水= 85/；^容量比） 中’獲得白色的析出物（共聚合物A_D-3)的沈殿。將沈 殿濾除，再次投入至與上述相同量的甲醇及水的混合溶劑 (曱醇/水= 95/5容量比）中，一邊攪拌一邊進行沈澱的清 洗。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。 於減壓下以40°C對該共聚合物濕粉進行約4〇小時乾 燥，獲得白色粉體（57.5 g)。 —然後，利用與GPC對所獲得的白色粉體進 行分析，並求出共聚合物整體的平均單體 及分子量分布（Mw/Mn)。另外，利2述刀方二 ^所獲㈣絲合物A_D_3的溶解性。將其結果示於表7。 U几蚀劑組成物的製造] 於上述所獲得的共聚合物A_D_3的·份中混合作為 沾，產生劑的三苯基疏三氟曱糾酸鹽2份、及作為溶劑 um ^ΕΑ 7CK) &amp;來製成均勻溶液。其後，利用孔徑為0.1 針對所2域11進行過濃，而製備抗侧組成物溶液。 將其忿:=劑組成物’利用上述方法評價感光度。 &lt;例A_D4:共聚合物Α-ΙΜ&gt;Then, the polymerization reaction solution in the flask was dropwise added to a mixed solvent of decyl alcohol and water (sterol/water = 85/; ^ capacity ratio) while stirring to obtain white precipitates (copolymerization). The hall of the object A_D-3). The chamber was filtered off, and again, it was poured into a mixed solvent of methanol and water (sterol/water = 95/5 capacity ratio) in the same amount as above, and the precipitate was washed while stirring. Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer wet powder was dried at 40 ° C under reduced pressure for about 4 hours to obtain a white powder (57.5 g). - Then, the obtained white powder was analyzed by GPC, and the average monomer and molecular weight distribution (Mw/Mn) of the entire copolymer were determined. In addition, the solubility of the (4) silk compound A_D_3 obtained by the knife 2 is obtained. The results are shown in Table 7. Manufacture of the composition of the U-etching agent] In the above-obtained portion of the copolymer A_D_3 obtained, 2 parts of triphenylphosphonium tribromide as a binder and a generating agent are mixed, and as a solvent um ^ ΕΑ 7CK) &amp; to make a homogeneous solution. Thereafter, the anti-side composition solution was prepared by subjecting the 2 domains 11 to an excessive concentration with a pore diameter of 0.1. The sensitivity was measured by the above method using 忿: = agent composition. &lt;Example A_D4: Copolymer Α-ΙΜ&gt;

Ill 201222146 含有單體（m_4)、單體u_5)、單體（ 3種早體的一種滴加溶液。 本例巾所個的各單體的合計量的莫耳比為uIll 201222146 contains monomer (m_4), monomer u_5), monomer (a kind of dropping solution of three kinds of early bodies. The molar ratio of the total amount of each monomer in this case is u

Cm-5) . (m-3) =33.9 ： 35.1 ： 3〇.ι 0 „境下，將乳酸乙㈣·6份、pGMEA42 6份 早體（m-4) L42份、單體（m_5) 8 $份加7與例A_D1相同的燒瓶中。將二 =厂邊對燒瓶⑽行麟—邊將水浴的溫度提ίΪCm-5) . (m-3) =33.9 : 35.1 : 3〇.ι 0 „By lactic acid B (4)·6 parts, pGMEA42 6 parts Early (m-4) L42 parts, monomer (m_5) 8 $ parts plus 7 in the same flask as in Example A_D1. The second = factory side to the flask (10) line - while the temperature of the water bath is raised

其後，自加入有乳酸乙酯65份鱼- 異丁叫上述的V6G1(商品名））2、==21氮雙 以固定速度_ 2G分鐘向燒瓶^ 2_·152 &amp; _加裝置， 的同日#，0+丄 &amp;瓶円進仃滴加。與該滴加處理 ri體^;ΐ單體（nM)_份、單體㈣咖3 份、二曱美Μ, 115伤乳酸乙醋38.6份、PGMEA45.1 氮雙異丁咖旨（上述的(商品名）)Thereafter, from the addition of 65 parts of ethyl lactate to the fish, the above-mentioned V6G1 (trade name) 2, ==21 nitrogen double at a fixed speed _ 2G minutes to the flask ^ 2 _ 152 &amp; _ add device, On the same day #, 0 + 丄 &amp; bottle into the 仃 drop. And the dropwise addition treatment ri body ^; ΐ monomer (nM) _ parts, monomer (four) coffee 3 parts, two 曱 曱 Μ, 115 injured lactic acid ethyl vinegar 38.6 parts, PGMEA45.1 nitrogen double diced coffee (the above (Product name))

轩心〇 、隹裝置，以固定速度歷時4小時向燒瓶内進 小時而，將水浴設為80〇C的溫度，並將燒瓶保持3 ¥A-D3相同的方式獲得白色的析出物（共 铲二^的沈澱，進行濾除、清洗、清洗後的濾除、 乾紐而獲付白色粉體（54.lg)。 〜η對:獲㈣共聚合⑯A&quot;0·4進行與例A_D3相同的測 疋及評價。將其結果示於表7。 &lt;例A E3 •共聚合物A-E-3〉 112 201222146 &quot;tuz.oopif 於例A-D3中，事先不將單體加入至燒瓶内，而私由 耳比^力7方式來合成絲合物。本射所使㈣單體^莫 耳比為（m-4):(m-5):(m-3) =35.0: 35.〇 :3〇〇。、 即’於氮氣環境下’將乳酸乙醋54·5份與pGMEA 23 3 二!7 ϋ與合成μ A·7 4目同的燒瓶中。將燒瓶放入至水浴 80°C。冑燒瓶内進㈣拌—邊將水浴的溫度提高至 繼、而’自加入有單體（m_4) 5117份、單體u_5) μ二===乳編则份、簡ea 品名心㈣異丁義（上述的犠（商 瓶内進行滴加。進而，^以固定速度歷時4小時向燒 將燒瓶保持3小時。吏切的溫度轉8G°C的狀態下 聚合的方式獲得白色的析出物(共 乾燥而獲得白色_ (仃麵、清洗、清洗後的渡除、 WM) g) 〇 對所獲得的共聚合物s 定及評價。將其結果示於表~E-3進行與例A_D2相同的測 &lt;例他共聚合物二4&gt; 於例A-D2中，事先 並藉由批量方式來合成共所有單體及溶劑加入至燒瓶内， 莫耳比為（m-4):(m、s^聚合物。本例中所使用的單體的 即，將乳酸乙酉旨 4 9^m_3) =36,0 : 32·0 : 32.0。 1.84 份、單體（m-5) 、PGMEA4.9份、單體（m_4) ’ 8份、單體（m_3) 2.27份、二曱 113 201222146 基-2,2M禹氮雙異丁酸酯（上述的V601 (商品名））1.725 份加入至25 mL的舒倫克燒瓶中後，以200 mL/分向溶液 内吹入氮氣1分鐘。繼而，將該燒瓶置於80°C的水浴上， 一邊攪拌一邊攪拌3小時。 繼而，一邊攪拌一邊將所獲得的反應溶液滴加至約10 倍量的曱醇中，獲得白色的析出物（共聚合物A-E-4)的 沈澱。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。 於減壓下以40°C對該共聚合物濕粉進行約40小時乾燥， 獲得白色粉體（6_1 g)。 對所獲得的共聚合物A-E-4進行與例A-D2相同的測 定及評價。將其結果示於表7。 &lt;例 A-F1&gt; 以下的共聚合物的評價是藉由依次進行本實施形態的 共聚合物評價方法的目標變數分析過程（I)、說明變數分 析過程（II)、模型精製過程（III)及樣品分析過程（IV)， 而求出各聚合物中的構成共聚合物的各單體中的同一種類 的單體的三單元組分率。 對合成例A-1〜合成例A-3中所獲得的均聚物A-A-1 〜均聚物A-A-3、合成例A-6〜合成例A-20中所獲得的共 聚合物A-B-1〜共聚合物A-B-15、合成例A-33〜合成例 A-37中所獲得的共聚合物A-C-1〜共聚合物A-C-5的合計 23種分別進行13C-NMR測定，而獲得光譜。再者，將測 定時的累計次數設為5000次，將FID處理時的零填滿設 為2次，將擴張因數設為2.0 Hz，將基峰設為氯仿 201222146 wzocpif (77.0ppm)，進行基線校正。 再者C-NMR測定是將氣化氯仿與氣化二甲基亞楓 的體積比50/50的混合溶劑用作溶劑，並 設為 40°C。 而且，自所獲得的錢光譜中，以G.l ppm的間隔對 源自聚合物的羰基碳的化學位移的顏，即175观沖m〜 179.00 ppm的範圍進行積分（峰值積分），而獲得4〇個積 φ 分值（目標變數分析過程、說明變數分析過程）。 另-方面，將聚合率為1〇%以内的共聚合物a b i〜 共聚合物A-B-15、共聚合物atj〜共聚合物A C 5的加 入組成，及上述所求出的共聚合反應性比代入至下述式的 各者中，分別求出共聚合物A_B-1〜共聚合物A-B-15、共 聚合物A-C-1〜共聚合物A_c_5中的3種單體單元三單元 組分率 P{111} (%)、P{222} (%)、P{333} (%)(目標變 數分析過程）。將其結果示於表2、表5。此處，單體單元 二單元組分率P {XXX}表示單體單元X中的同一種類的單 Φ 體單元的三單元組分率。Xuan Xin 〇, 隹 device, at a fixed speed for 4 hours into the flask into the hour, set the water bath to a temperature of 80 ° C, and maintain the flask in the same way as 3 ¥ A-D3 to obtain white precipitate (total shovel Precipitation of ii, filtration, washing, washing, and white powder (54.lg). ηη: obtaining (4) copolymerization 16A&quot;0·4 is the same as example A_D3 The results are shown in Table 7. &lt;Example A E3 • Copolymer AE-3> 112 201222146 &quot;tuz.oopif In Example A-D3, the monomer was not added to the flask in advance. The silk is synthesized by the ear by the method of the force 7 method. The atomic ratio of the (4) monomer is (m-4): (m-5): (m-3) = 35.0: 35. :3〇〇., that is, 'under nitrogen atmosphere', 54. 5 parts of lactic acid ethyl acetate and pGMEA 23 3 bis! 7 ϋ and the synthetic μ A·7 4 mesh in the same flask. The flask was placed in a water bath 80 ° C. The inside of the flask is filled with (four) mixing - while the temperature of the water bath is increased, and 'self-added monomer (m_4) 5117 parts, monomer u_5) μ two === dairy code, simple ea product name (four) Iso Dingyi (the above 犠 (the drop in the bottle) Further, the flask was kept at a fixed speed for 4 hours, and the flask was kept for 3 hours. The white precipitate was obtained by polymerization in a state where the temperature of the tangent was changed to 8 G ° C (co-drying to obtain white _ (kneading, washing, After washing, WM) g) 〇 Determine and evaluate the obtained copolymer s. The results are shown in Table ~E-3 and the same test as in Example A_D2. Example: Copolymer 2 4 In Example A-D2, a total of all monomers and a solvent were synthesized in advance by batch method, and the molar ratio was (m-4): (m, s ^ polymer. used in this example) For the monomer, lactic acid is intended to be 4 9^m_3) = 36, 0: 32·0: 32.0. 1.84 parts, monomer (m-5), PGMEA 4.9 parts, monomer (m_4) '8 parts, Monomer (m_3) 2.27 parts, dioxime 113 201222146 base-2, 2M hydrazine diisobutyrate (V601 (trade name) above) 1.725 parts was added to a 25 mL Schlenk flask to 200 mL / The nitrogen gas was blown into the solution for 1 minute. Then, the flask was placed in a water bath at 80 ° C, and stirred for 3 hours while stirring. Then, the obtained reaction solution was added dropwise while stirring. A precipitate of white precipitate (copolymer AE-4) was obtained in about 10 times the amount of sterol. Then, the washed precipitate was filtered off to obtain a copolymer wet powder. 40 ° C under reduced pressure. The copolymer wet powder was dried for about 40 hours to obtain a white powder (6_1 g). The obtained copolymer A-E-4 was subjected to the same measurement and evaluation as in Examples A to D2. The results are shown in Table 7. &lt;Example A-F1&gt; The following evaluation of the copolymer was carried out by sequentially performing the target variable analysis process (I) of the copolymer evaluation method of the present embodiment, explaining the variable analysis process (II), and the model refining process (III). And the sample analysis process (IV), and the triad component ratio of the same kind of monomer among the monomers constituting the copolymer in each polymer is determined. The copolymers AA-1 to H4A obtained in Synthesis Examples A-1 to A-3, and the copolymer AB- obtained in Synthesis Example A-6 to Synthesis A-20 were synthesized. The total of 23 kinds of the copolymers AC-1 to the copolymer AC-5 obtained in 1 to the copolymer AB-15, Synthesis Examples A-33 to Synthesis A-37 were each subjected to 13 C-NMR measurement, and obtained. spectrum. In addition, the cumulative number of times during the measurement was 5000 times, the zero filling at the time of FID processing was set to 2 times, the expansion factor was 2.0 Hz, and the base peak was chloroform 201222146 wzocpif (77.0 ppm), and the baseline was made. Correction. Further, in the C-NMR measurement, a mixed solvent of vaporized chloroform and vaporized dimethyl sulfoxide in a volume ratio of 50/50 was used as a solvent, and it was set to 40 °C. Moreover, from the obtained spectrum of money, the range of the chemical shift of the carbonyl carbon derived from the polymer, that is, the range of 175 Å to 179.00 ppm is integrated (peak integration) at intervals of Gl ppm, and 4 获得 is obtained. The product φ score (the target variable analysis process, explaining the variable analysis process). On the other hand, the addition ratio of the copolymer abi to the copolymer AB-15, the copolymer atj to the copolymer AC 5 having a polymerization ratio of 1% or less, and the copolymerization reactivity ratio determined as described above Substituting into each of the following formulas, the three-unit component ratios of the three monomer units in the copolymer A_B-1 to the copolymer AB-15, the copolymer AC-1 to the copolymer A_c_5, respectively, were determined. P{111} (%), P{222} (%), P{333} (%) (target variable analysis process). The results are shown in Table 2 and Table 5. Here, the monomer unit two unit component ratio P {XXX} represents the three unit composition ratio of the same type of single Φ body unit in the monomer unit X.

Pll = [Ml]/ ( [Ml] + [Ml]/rl2 + [Ml]/rl3 ) P22 = [M2]/ ( [Ml]/r21 + [Ml] + [Ml]/r23 ) P33 = [M3]/ ( [Ml]/r31 + [Ml]/r32 + [Ml]) 115 201222146 P{111} (〇/0) =i〇〇x[]V[l']xPllxPll P{222} (〇/0) = i〇〇x[M2,]xP22xP22 P{333} (〇/〇) =i〇〇x[M3']xP33xP33 此處’當成長末端上存在m-1、m-2、m-3時，Pll、 P22、P33分別為與m_i、m_2、m_3進行反應的概率，[μ】]、 [M2]、[M3]分別為m_i、m_2、m-3的加入組成比，[μγ]、 [M2’]、[M3’]的共聚合組成比。 繼而’利用例如Pattern Recognition System公司製造 的Sirius(註冊商標）作為多變量分析軟體，將均聚物α_α· i 〜均聚物A-A-3、共聚合物A-B-1〜共聚合物A-B-15、共 聚合物A-C-1〜共聚合物Α_〇5的關於羰基碳的合計92〇 個積分值δ又為說明變量側，將3種單體單元三單元組分 P{111} ( %)、Ρ{222} ( % )、ρ{333} ( %)設為目標變量側， 使用部分最小平方法（PLS法）來構築實驗模型（模型生 成過程）。於本實施形態中，使用莫耳％，但記載為％。 而且’於該實驗模型中，使用例A_D1〜例A_D2、例 A-E1〜例A-E2中所獲得的共聚合物a-D-Ι〜共聚合物 A-D-2及共聚合物A-E-1〜共聚合物A-E-2的關於幾基碳 的合計160個積分值，藉由以下的多變量分析軟體來算出 二單元組分率（樣品分析過程）。此處，利用例如pattern Recognition System公司製造Sirius (註冊商標）作為多變 116 201222146 wzeepif 量分析軟體，並使用本實施形態的共聚合物評價方法中所 說明的部分最小平方法（PLS法），求出3種的各單體單元 的同一種類的單體單元的三單元組分率預測值（％)。將其 結果不於表7。 &lt; 例 A-F2 &gt; 與本實施形態的共聚合物評價方法中所說明的處理， 即例A-F1的記載同樣地，算出共聚合物的組成中的同— 種類的單體單元的三單元組分率。對合成例A-3〜合成例 A-5中所獲得的均聚物a_A_3〜均聚物A-A-5、合成例A_2 j 〜合成例A-32中所獲得的共聚合物Α·Β_16〜共聚合物 Α-Β-27、合成例Α_38〜合成例Α_42中所獲得的共聚合物 A_C-6〜共聚合物A-C-10的合計20種分別進行13C_NMr 測定，而獲得nmr光譜信號。 再者’將測定時的累計次數設為5000次，將fid處 理時的零填充設為2次，將擴張因數設為2.0 Hz，將基峰 ，，氯仿（77.0Ppm)，進行基線校正。再者，uc_NMR測 $是將氛化氯仿與氘化二甲基亞颯的體積比50/50的混合 /谷劑用作溶劑，並將測定溫度設為4〇。〇。 而且’自所獲得的各個光譜中，以0.1 ppm的間隔對 ，自聚合物的羰基碳的175.00 ppm〜179.00 ppm的範圍進 行積刀，而獲得4〇個積分值（目標變數分析過程、說明變 數分析過程）。 ^與例A_F1相同的方式’分別求出共聚合物A-B-16 〜共聚合物A-B-27、共聚合物A-C-6〜共聚合物A_c_1〇 117 201222146 中的3種三單元組單體（單元）鏈分率P{444}(%)、!&gt;{555} (%)、P{333} (%)(目標變數分析過程）。將其結果示於 表3、表6。 繼而，將均聚物A-A-4〜均聚物A-A-5、共聚合物 A-B-16〜共聚合物A-B-27、共聚合物A-C-6〜共聚合物 A-C-10的關於魏基碳的合計800個積分值設為說明變量 侧，將3種三單元組單體（單元）鏈分率P{444} (%)、 P{555} (%)、P{333} (%)設為目標變量側，使用部分最 小平方法（PLS法）來構築實驗模型（模型生成過程）。 而且，於該實驗模型中，使用例A-D3〜例A-D4、例 A-E3〜例A-E4中所獲得的共聚合物A-D-3〜共聚合物 A-D-4及共聚合物A-E-3〜共聚合物A-E-4的關於羰基碳 的合計X160個積分值，藉由本實施形態的共聚合物評價方 法，並利用部分最小平方法（PLS法）求出3種的各單體 單元的三單元組分率預測值（％ )(樣品分析過程）。將其 結果示於表7。Pll = [Ml]/ ( [Ml] + [Ml]/rl2 + [Ml]/rl3 ) P22 = [M2]/ ( [Ml]/r21 + [Ml] + [Ml]/r23 ) P33 = [M3 ]/ ( [Ml]/r31 + [Ml]/r32 + [Ml]) 115 201222146 P{111} (〇/0) =i〇〇x[]V[l']xPllxPll P{222} (〇/ 0) = i〇〇x[M2,]xP22xP22 P{333} (〇/〇) = i〇〇x[M3']xP33xP33 where 'when m-1, m-2, m-3 exist at the end of growth When Pll, P22, and P33 are the probabilities of reacting with m_i, m_2, and m_3, respectively, [μ], [M2], and [M3] are the composition ratios of m_i, m_2, and m-3, respectively, [μγ], The copolymerization composition ratio of [M2'] and [M3']. Then, using Sirius (registered trademark) manufactured by, for example, Pattern Recognition System, as a multivariate analysis software, homopolymer α_α· i to homopolymer AA-3, copolymer AB-1 to copolymer AB-15, The total of 92 〇 integral values δ of the copolymers AC-1 to the copolymer Α_〇5 with respect to the carbonyl carbon is again the explanatory variable side, and the three monomer units three unit components P{111} (%), Ρ{222} ( % ) and ρ{333} ( %) are set to the target variable side, and the experimental model (model generation process) is constructed using the partial least squares method (PLS method). In the present embodiment, mol% is used, but it is described as %. Moreover, in the experimental model, the copolymers aD-Ι~copolymer AD-2 and the copolymer AE-1~ obtained in Example A_D1~Example A_D2, Example A-E1~Example A-E2 were used. The total integral value of the polymer AE-2 with respect to several base carbons was calculated by the following multivariate analysis software (sample analysis process). Here, for example, Sirius (registered trademark) manufactured by Pattern Recognition System Co., Ltd. is used as the versatile 116 201222146 wzeepif amount analysis software, and the partial least squares method (PLS method) described in the copolymer evaluation method of the present embodiment is used. The predicted value (%) of the triad fraction of the same type of monomer unit of each of the three kinds of monomer units. The results are not shown in Table 7. &lt;Examples A-F2 &gt; In the same manner as described in Example A-F1, the treatment described in the method for evaluating a copolymer of the present embodiment, the same type of monomer unit in the composition of the copolymer was calculated. Three unit component rate. The copolymers a_A_3 to homopolymer AA-5 obtained in Synthesis Examples A-3 to Synthesis A-5, and the copolymers obtained in Synthesis Examples A_2 j to Synthesis A-32 were a total of 共·Β_16~ In the polymer Α-Β-27, the total of 20 kinds of the copolymer A_C-6 to the copolymer AC-10 obtained in the synthesis example Α_38 to the synthesis example Α42, 13C_NMr was measured, and the nmr spectrum signal was obtained. Further, the cumulative number of times at the time of measurement was 5,000 times, the zero padding at the time of fid processing was set to 2 times, the expansion factor was set to 2.0 Hz, and the base peak and chloroform (77.0 Ppm) were subjected to baseline correction. Further, the uc_NMR measurement was carried out by using a 50/50 volume/mix of a volume ratio of chloroform to deuterated dimethyl hydrazine as a solvent, and the measurement temperature was set to 4 Torr. Hey. Moreover, 'from each spectrum obtained, at a spacing of 0.1 ppm, from the range of 175.00 ppm to 179.00 ppm of the carbonyl carbon of the polymer, to obtain 4 integral values (target variable analysis process, explanatory variable) Analysis process). ^ In the same manner as in Example A_F1, three triad monomers (units in the copolymer AB-16 to the copolymer AB-27, the copolymer AC-6 to the copolymer A_c_1〇117 201222146, respectively, were determined. ) Chain rate P{444} (%), !&gt;{555} (%), P{333} (%) (target variable analysis process). The results are shown in Tables 3 and 6. Then, the homopolymer AA-4~Homopolymer AA-5, the copolymer AB-16~the copolymer AB-27, the copolymer AC-6~the copolymer AC-10, the Wei-based carbon The total of 800 integral values is set to the explanatory variable side, and the three triads (unit) chain fractions P{444} (%), P{555} (%), and P{333} (%) are set. On the target variable side, a partial least squares method (PLS method) is used to construct an experimental model (model generation process). Further, in this experimental model, the copolymer AD-3 to the copolymer AD-4 and the copolymer AE obtained in Examples A-D3 to A-D4, and Examples A-E3 to A-E4 were used. -3 to the total of X160 integral values of the carbonyl carbon of the copolymer AE-4, and the three kinds of monomer units were determined by the partial least squares method (PLS method) by the copolymer evaluation method of the present embodiment. The predicted value of the three-unit component rate (%) (sample analysis process). The results are shown in Table 7.

118 201222146118 201222146

J-aooooi 鬥(Nd 崩 'Ί IS m CO m '-V-- Ct, 76.2 38.5 14.6 &lt;N ΓΛ d d 卜 CN 12.8 73.6 ?Γ (N CN '-w ft. 59.5 19.6 m *ri Os o o o o 寸 ΓΟ 15.3 39.5 76.9 W-* Ph m 〇 CN 21.8 47.0 80.6 ! 75.0 | ! 37.1 — ro d 3 i1 si — w-i m cs CO 00 00 〇 卜 »ri 卜 CO 〇\ od cn od 00 00 共聚合組成比/mol% j m έ ON 00 1 74.0 | 47.0 | 29.3 1 卜 00 ON 1 29.4 49.2 69.7 90.0 m-2 84.5 ! 1 _ 59.4 I 〇6 m 1 22,5 —I 1 10-9 1 | 26.0 | 53.0 | 70.7 | 91.3 1 s 15.5 40.6 61.9 77.5 | 92.3 | CN Os 70.6 50.8 30.3 10.0 加入單體組成比/mol% ΓΛ έ § o o o o § 1_^_1 § o o 〇 o 1 ε o o § o o cn έ I 6.37 I 4.96 3.54 1 2.12 I 0.71 0.71 | 2.12——」 1 3.54 I 4.96 6.37 饀 &lt; -¾ m-2 5.29 4.12 2.94 1.76 0.59 0.59 2.94 4.12 5.29 1 s 0.51 1 2.55 1 3.57 4.59 4.59 3-57 I 1 2.55 1.53 0.51 共聚合 A-B-l A-B-2 ί A-B-3 | A-B-4 I | A-B-5 | I A-B-6 I I A-B-7 ] 1 A-B-8 I I A-B-9 I I A-B-10 I | A-B-l 1 | I A-B-l2 I 1 A-B-l3 I I A-B-14 I A-B-l 5 201222146 JU008S 寸 te &lt;】 單體三單元組分率 m '-y-&lt; PL, 61.7 30.8 12.3 cs o o 〇〇 26.5 58.3 &lt;-ν— (1η 14.2 On (N U-ϊ 〇 o o CN 〇 CN CN 〇\ 31.5 寸 w-* CU &lt;N 12.6 31.6 60.3 63.6 32.3 q in i產率/% 1 〇 寸* cs 寸· m — vd m 〇\ 寸· — 〇\ 〇6 〇6 00 VO 共聚合組成比/mol% CO έ I 83.2 I | 72.3 | 1 51.3 I m 1— 17^_J | 39.7 ] I 66.2 | | 82.5 | m-5 I 60.6 I 1 41.8. J L 28.4 I 丨 14.2 I I 16.8 I | 27.7 I 1 48.7 I I 68.9 I m-4 39.4 ! 58.2 i 71.6 I 85.8 I I 83.0 I I 60.3 I I 33.8 I 1 17.5 i加入單艘組成比/mol% | m-3 I g 3 o o s g tn έ g s o 〇 s g m-4 o § § g § o CO έ I 5.66 I I 4.25 I I 2.83 I | 1.42 I | 1.42 | I 2.83 I 1 4.25 5.66 雖 ϊΐ- &lt; 6 I 5.95 I | 4.46 I I 2.98 I | 1_49 I 1 1-49 I I 2.98 I I 4.46 I I 5.95 I m-4 I 1.02 I 2.04 | 3.06 I | 4.08 I I 4.08 I 丨 3.06 I 2.04 1 s 共聚合物 A-B-16 A-B-17 A-B-18 A-B-19 A-B-20 A-B-21 A-B-22 A-B-23 A-B-24 A-B-25 A-B-26 A-B-27 201222146J-aooooi bucket (Nd collapse 'Ί IS m CO m '-V-- Ct, 76.2 38.5 14.6 &lt;N ΓΛ dd 卜 CN 12.8 73.6 Γ (N CN '-w ft. 59.5 19.6 m *ri Os oooo inch ΓΟ 15.3 39.5 76.9 W-* Ph m 〇CN 21.8 47.0 80.6 ! 75.0 | ! 37.1 — ro d 3 i1 si — wi m cs CO 00 00 〇 » »ri 卜 CO 〇 od od 00 00 Copolymerization composition ratio / Mol% jm έ ON 00 1 74.0 | 47.0 | 29.3 1 00 ON 1 29.4 49.2 69.7 90.0 m-2 84.5 ! 1 _ 59.4 I 〇6 m 1 22,5 —I 1 10-9 1 | 26.0 | 53.0 | 70.7 91.3 1 s 15.5 40.6 61.9 77.5 | 92.3 | CN Os 70.6 50.8 30.3 10.0 Adding monomer composition ratio / mol% ΓΛ § § oooo § 1_^_1 § oo 〇o 1 ε oo § oo cn έ I 6.37 I 4.96 3.54 1 2.12 I 0.71 0.71 | 2.12——” 1 3.54 I 4.96 6.37 饀&lt; -3⁄4 m-2 5.29 4.12 2.94 1.76 0.59 0.59 2.94 4.12 5.29 1 s 0.51 1 2.55 1 3.57 4.59 4.59 3-57 I 1 2.55 1.53 0.51 Copolymerization ABl AB-2 ί AB-3 | AB-4 I | AB-5 | I AB-6 II AB-7 ] 1 AB-8 II AB-9 II AB-10 I | A- Bl 1 | I AB-l2 I 1 AB-l3 II AB-14 I ABl 5 201222146 JU008S inch te &lt;] monomer triad fraction rate m '-y-&lt; PL, 61.7 30.8 12.3 cs oo 〇〇 26.5 58.3 &lt;-ν- (1η 14.2 On (N U-ϊ 〇oo CN 〇CN CN 〇\ 31.5 inch w-* CU &lt;N 12.6 31.6 60.3 63.6 32.3 q in i yield /% 1 inch * cs inch · m — vd m 〇 — — 〇 6 〇 6 00 VO Copolymerization composition ratio / mol% CO έ I 83.2 I | 72.3 | 1 51.3 I m 1— 17^_J | 39.7 ] I 66.2 | | 82.5 | m-5 I 60.6 I 1 41.8. JL 28.4 I 丨14.2 II 16.8 I | 27.7 I 1 48.7 II 68.9 I m-4 39.4 ! 58.2 i 71.6 I 85.8 II 83.0 II 60.3 II 33.8 I 1 17.5 i Adding a single ship Ratio / mol% | m-3 I g 3 oosg tn έ gso 〇sg m-4 o § § g § o CO έ I 5.66 II 4.25 II 2.83 I | 1.42 I | 1.42 | I 2.83 I 1 4.25 5.66 &lt; 6 I 5.95 I | 4.46 II 2.98 I | 1_49 I 1 1-49 II 2.98 II 4.46 II 5.95 I m-4 I 1.02 I 2.04 | 3.06 I | 4.08 II 4.08 I 丨 3.06 I 2.04 1 s Copolymer AB -16 AB-17 A- B-18 A-B-19 A-B-20 A-B-21 A-B-22 A-B-23 A-B-24 A-B-25 A-B-26 A-B-27 201222146

【寸^】 1.484 0.583 1.229 1.190 1.040 1.109 1.313 0.239 0.517 1.410 1.348 1.617 CN 3 CO CN °2 CO 1—H t m ro U cn t x\sL s fn cn m w- PL, o o Os o o Os cS 單體三單元组分名 式 ?r (N (N w- 〇H OO 卜 寸 ΓΟ CO 寸· CN ψ—* w- Ph rn — fN iri ! 10.8 15.6 18.5 產率 — m CN ϊ&gt; m oo 共聚合組成比/mol% 1 m-3 I 1 41.2 | I 22.3 I 23-5 1 ! 12.2 23.5 | m-2 I L 24.11 1 42.6 I L—2[1」 1 36.7 I ! 16.9 »—H 1 6 1.34.7 1 H cn | 48.4 I ψ—i 59.6 加入單體組成比/mol% cn έ o o 1 m-2 I o 1 B o ^bX) S 1 2.83 1 1 1.42 1 LJ-42_J 0_71 I 1.42 韜 &lt; | m-2 I ―丄 76—— 1 2-94 1 1 2.35 I 2.65 1.76 1 B 1 1.53 1 I 1.53 1 1— 2.04 1 | 2.30 I 2.55 S 0 A-C-l A-C-2 A-C-3 A-C-4 A-C-5 201222146 J'aooooCNo 寸 鬥 m m cn ST 16.8 CO — 00 rn »—H o 單體三單元組分马 IT) m PU &lt;N 〇 V〇 cs v〇 〇 o cn o 式 /··*» 5 Si cn ΓΛ fS v〇 〇6 16.4 20.9 相jj 是 yn 寸· in CN 卜_ cn od 共聚合组成比/mol% CO έ o d 〇 〇 〇 〇 o d o d ^T) έ | 84.5 I 1 5941 | 38.1 I 1 22.5 I 卜 m-4 1 15.5 I I 40.6 I | 61.9 I 1 77.5 I 92.3 加入單體組成比/mol% ΓΟ έ o &lt; in έ fM m $ j m-4 &lt;T) &lt;N |TJ -S? |__m-3_J I 3.54 I 1 2.12 I 1 2.12 I | 0.71 I 丨 1.42 1 雜 in έ 1 1.86 I 3.72 I | 2.60 I 1 3.35 I 1 2.23 1 m-4 1.28 I | 1.02 I | 1.79 I I 2.30 I 1 2.55 1 共聚合物 A-C-6 A-C-7 A-C-8 A-C-9 A-C-10 鬥卜蟮】 感光度 /mJ，cm2 1.01 1.21 0.51 0.54 v〇 無法評價 0.78 無法評價 溶解性 /分鐘| (N 户H 卜 ON CN m 1有殘渣1 00 1有殘渣1 單體三單元組分率預測值 合計值| 12.7 1 1 115 | 1 _ .12,6 1 | 22.3 1 1 33.5 1 1 22.4 1 35.0 1 P{555}% r^i 寸 cn Os 19.4 ρΓ CN in yn οό Ρ{333}% m ro cn o — — o od 10.1 00 \〇 Ρ{222}% rn &lt;〇· oo 00 Ρ{111}% O) — C) — σ\ 1 17.6 1 分子量 Mw/Mn yr) I 1.66 I On | 1.75 I L—2.21 I 1 1-78 I 2.05 Mw o 沄 o' o o o' o 气 ocT o &lt;N oo&quot; o g 10,000 I 7,400 I 7,500 冷聚合组成比/mol% έ CN CN m m m CO m-4 卜 m P； Ρ； m-3 I O\ m 寸 00 rs m-2 o 寸 Q\ m ο 1 ε o o |共聚| 合物 I A-D-l I I A-D-2 I 1 A-D-3 I I A-D-4 I I A-E-l I 1 Α-Ε-2 I A-E-3 I 1 Α-Ε-4 1 ·SI · 201222146 wzospif -種類^單可知於共聚合物的組成中的同 /丨、，佶用轉此取兀二單元組分率的預測值的合計值越 解性越高^、Λ合物所製備的抗蝴組成物的感光度與溶 。即j表7所示’可知糊同—種_單體單元的三 早^^料糊值的合計健於Μ (%)，較佳為低於 15^/〇)的例A_D1〜例A_D4中所獲得的共聚合物所製備[inch^] 1.484 0.583 1.229 1.190 1.040 1.109 1.313 0.239 0.517 1.410 1.348 1.617 CN 3 CO CN °2 CO 1—H tm ro U cn tx\sL s fn cn m w- PL, oo Os oo Os cS single unit The composition name is ?r (N (N w- 〇H OO ΓΟ inch ΓΟ CO 寸 · CN ψ—* w- Ph rn — fN iri ! 10.8 15.6 18.5 Yield — m CN ϊ&gt; m oo Copolymerization composition ratio / Mol% 1 m-3 I 1 41.2 | I 22.3 I 23-5 1 ! 12.2 23.5 | m-2 IL 24.11 1 42.6 IL—2[1” 1 36.7 I ! 16.9 »—H 1 6 1.34.7 1 H cn 48.4 I ψ—i 59.6 Adding monomer composition ratio/mol% cn oo oo 1 m-2 I o 1 B o ^bX) S 1 2.83 1 1 1.42 1 LJ-42_J 0_71 I 1.42 韬&lt; | m-2 I ―丄76—— 1 2-94 1 1 2.35 I 2.65 1.76 1 B 1 1.53 1 I 1.53 1 1— 2.04 1 | 2.30 I 2.55 S 0 ACl AC-2 AC-3 AC-4 AC-5 201222146 J' aooooCNo inch mm cn ST 16.8 CO — 00 rn »—H o monomer three-unit component horse IT) m PU &lt;N 〇V〇cs v〇〇o cn o type /··*» 5 Si cn ΓΛ fS V〇〇6 16.4 20.9 phase jj is yn inch · in CN _ cn od copolymerization composition ratio / mol% CO έ od 〇〇〇〇odod ^T) έ | 84.5 I 1 5941 | 38.1 I 1 22.5 I 卜 m-4 1 15.5 II 40.6 I | 61.9 I 1 77.5 I 92.3 Adding monomer composition ratio / mol% ΓΟ έ o &lt; in έ fM m $ j m-4 &lt;T) &lt;N |TJ -S? |__m-3_J I 3.54 I 1 2.12 I 1 2.12 I | 0.71 I 丨1.42 1 Miscellaneous in έ 1 1.86 I 3.72 I | 2.60 I 1 3.35 I 1 2.23 1 m-4 1.28 I | 1.02 I | 1.79 II 2.30 I 1 2.55 1 Copolymer AC-6 AC-7 AC-8 AC-9 AC-10 Buddy] Sensitivity / mJ, cm2 1.01 1.21 0.51 0.54 v〇 could not be evaluated 0.78 Solubility/minutes could not be evaluated | (N Household H Bu ON CN m 1 Residue 1 00 1 Residue 1 Total value of monomer triad fraction prediction value | 12.7 1 1 115 | 1 _ .12,6 1 | 22.3 1 1 33.5 1 1 22.4 1 35.0 1 P{555}% r^i inch cn Os 19.4 ρΓ CN in yn οό Ρ{333}% m ro cn o — — o od 10.1 00 \〇Ρ{222}% rn &lt;〇· oo 00 Ρ{111}% O) — C) — σ\ 1 17.6 1 MMW/Mn yr) I 1.66 I On | 1.75 IL—2.21 I 1 1-78 I 2.05 Mw o 沄o' ooo' o gas ocT o &lt;N oo&quot; og 10,000 I 7,400 I 7,500 Cold polymerization composition ratio / mol% έ CN CN mmm CO m-4 卜 m P; Ρ; m-3 IO\ m inch 00 rs m-2 o inch Q\ m ο 1 ε oo | copolymerization | compound I ADl II AD-2 I 1 AD-3 II AD-4 II AEl I 1 Α-Ε-2 I AE-3 I 1 Α-Ε-4 1 ·SI · 201222146 wzospif - type ^ single is known in the composition of the copolymer The same as the total value of the predicted values of the two unit components, the higher the resolution, the sensitivity and dissolution of the anti-butter composition prepared by the composition. That is, in the case of the table A, the total value of the three-times of the monomer unit is shown in Table A_D1 to Example A_D4 in which the total value of the paste value of the monomer unit is 健 (%), preferably less than 15^/〇. Preparation of the obtained copolymer

的抗。#齊丨、’、_£成物的感光度及溶解性優於彳㈣該合計值超過 20 (%) ’ 佳為超過15 (%)的共聚合物所製備的抗钱劑 組成物。 另一方面’同一種類的單體單元的三單元組分率的合 5十值超過30 (%)者於溶解性方面殘留有殘渣，對於光照 射的感光度的測定亦因該殘渣殘留而無法進行。因此，可 知同一種類的單體單元的三單元組分率的合計值超過3〇 (°/〇)的共聚合物無法用於微影製程步驟中所使用的抗蝕 劑組成物的製備。 如上所述’根據表7可明確利用本實施形態的共聚合 物評價方法所求出的共聚合物中的三單元組分率的數值、 與自該共聚合物所製備的抗蝕劑組成物的溶解性及感光度 的關聯南。 因此’藉由合成共聚合物，並利用本實施形態的共聚 合物評價方法算出三單元組分率，而可省略實際製作抗蝕 劑組成物來進行溶解性及感光度的評價的步驟，並可簡單 地設定抗餘劑組成物的製備所需的共聚合物的製造方法及 123 201222146 單體的調整量。 另外，控制部18將三單元組分率 合計值的彻共聚合物所製備的抗㈣丨°^ '與對應於 (溶解性及感光度）的對應關係儲存於内部成的特性值 儲^部16中，並將其讀出），並根據未知樣品的Τϊ定於 /刀率的合計值，推斷利用未知樣 [早输 成物的特性值。 ，、眾σ物所製備的組 本實施形態的評價方法較佳為更包 程：控制部具有三單元組分率的合計值^^控制過 並根據未知樣品的三單元組分==值=關 未知樣品的共聚合物所製備的組成物的特性值。斷利用 另外，本實施形態的共聚合物的評價方法較 4合物為微影製侧共聚合物， 心述 組成物，上述組成物的特性值物且為微衫製程 性或對於光照射的感光度/組成物對於溶劑的溶解 ，如，當鮮導《置的製造巾生成圖轉， 步驟=^^定光度及溶解性的上限值由微影製程 ^感光度及溶解性的上限值作為臨限值，將超過該 值組分率的合計值作為三單元組分率極限 值，並事先設定於儲存部16中。 :且’將製備過程中的各單體的調整量及製造方法試 丁夕:人，如已說明般根據自NMR測定所獲得的測定值， 124 201222146 HUZOOpif 去來求出進行該試行所獲得的共聚合物的Resistance. #齐丨, ', _£ The sensitivity and solubility of the finished product are better than that of the 彳 (4) the total amount of the anti-money composition prepared by the copolymer of more than 20 (%) ‘more than 15 (%). On the other hand, in the case where the ratio of the three-component fraction of the same type of monomer unit exceeds 30 (%), the residue remains in the solubility, and the measurement of the sensitivity of light irradiation cannot be caused by the residue remaining. get on. Therefore, it is known that a copolymer having a total triblock fraction ratio of the same kind of monomer unit exceeding 3 Å (°/〇) cannot be used for the preparation of the resist composition used in the lithography process step. As described above, the numerical value of the triad component ratio in the copolymer obtained by the copolymer evaluation method of the present embodiment and the resist composition prepared from the copolymer can be clearly determined from Table 7 The solubility and sensitivity of the correlation south. Therefore, by synthesizing the copolymer and calculating the triad fraction by the copolymer evaluation method of the present embodiment, the step of actually preparing the resist composition for evaluation of solubility and sensitivity can be omitted, and The method of producing the copolymer required for the preparation of the anti-residue composition and the adjustment amount of the 123 201222146 monomer can be easily set. Further, the control unit 18 stores the resistance relationship between the anti-(tetra) ^^^ prepared by the total copolymer of the three-unit component ratio and the corresponding relationship (solubility and sensitivity) in the internal characteristic value storage unit. In the 16th, and read it out, and based on the total value of the unknown sample and the / knife rate, it is inferred that the characteristic value of the early sample is used. The evaluation method of the present embodiment is preferably a further package: the control unit has a total value of the three-element component ratio and is controlled according to the three-element component of the unknown sample == value = The characteristic value of the composition prepared by the copolymer of the unknown sample. Further, the evaluation method of the copolymer of the present embodiment is a micro-sharing side copolymer, a composition of the composition, and a characteristic value of the composition, and is a micro-shirt process or light irradiation. Sensitivity of the sensitivity/composition of the solvent, for example, when the fresh guide is used to create a pattern, the step = ^ ^ the upper limit of the luminosity and solubility is determined by the lithography process ^ sensitivity and solubility limit The value is a threshold value, and the total value exceeding the component rate of the value is taken as the three-unit component rate limit value, and is set in the storage unit 16 in advance. : and 'the amount of adjustment of each monomer in the preparation process and the manufacturing method. Measured by the NMR measurement as described, 124 201222146 HUZOOpif to obtain the obtained test. Copolymer

藉由PLS 單元 組分率，並自進行試行所生成的共聚合物中，選 組分率的合計值為三單元組分率極紐以下的共聚^凡 藉此可簡單崎備感光度及轉性兩 二 劑組成物。 k增抗姓 此處，控㈣18將内部所設定的三單元組By using the PLS unit component ratio and the copolymer obtained from the trial, the total of the selected component ratios is the copolymerization of the three-component fraction, which is simple and reliable. Sex two or two agent composition. k increase anti-surname here, control (four) 18 will set the internal triad

與所獲得的三單元組分率的合計值加以比較，並進行戶= 得=共聚合物的特性是否為適合於抗_組成物的特性^ 判定。 即’控制部18於所獲得的三單元組分率的合計值小於 三單元組分率極限㈣情況下，狀為適合於抗餘劑组成 物的製備，於所獲得的三單元組分率的合計值超過三單元 址分率極限值的情況下，判定為不適合抗㈣組成物的製 備，並針對各聚合物將判定結果顯示於顯示部17中。&lt; 使用如上述般製備的抗蝕劑組成物，於基板，例如半 導體基板上形成抗蝕圖案，藉此可實現對應於曝光遮罩的 微細圖案的微細的加工精度。 即，可進行被加工基板上形成有圖案的基板的製造， 该製造包括：將抗蝕劑組成物塗佈於被加工基板上的步 驟、利用250 nm以下的波長的光進行曝光的步驟、以及 利用顯影液進行顯影的步驟。 此處，設定為250 nm以下的波長是為了與本實施形 態的抗蝕劑組成物使用KrF準分子雷射（波長：248 nm)、 ArF 準分子雷射（波長：193 nm )、EUV ( Extreme 125 201222146 論極紫外線）光的準分子雷射（波長：13 nm) 等作為=照射的光的微影製程技術相對應。 本實施形態中的抗姓劑組成物作為可較佳地對廡於照 射光的短波長化及圖案的微細化的抗触劑組成物，是含有 酸脫離性基藉由酸的作用脫離而成為驗可溶性的聚合物、 及光酸產生劑的所謂的化學增幅型抗侧組成物。 a物f T本實施形態的抗蝕劑組成物的製備的共聚 1單元组分_=求出般n種類的上述單體單元的 佳為1 = S十於共聚合物中設為2〇莫耳％以下，較 莫耳％以下，更佳為設為i3 β 又疋二早兀組分率極限值。 照射而產生酸的Γ合藉物由來ΐ備射線（光的照射）或放射線的 途的==:!::_:於使半導體製造用 行聚體1體〜（11為2以上的整數）進 (構：)單^!=;丨:輸此出的單體 聚合物進行評價昧㈣Λ成）％的微影製程用共 單元組分率的t:於單體單元的三 為該判定的為1 合於微影製程組成物的製備。成 合計較佳^5^1 料料摘三單元組分率的 =為15莫耳％以下，更佳為13莫耳％以下 者’儲存部16是設為包含硬碟裝置或磁光碟裝置、 126 201222146 H-UZO〇pif 快閃記憶體等非揮發性的記憶體、縣獨光碟⑽ Disc Read Only Memory ’ CD-ROM)等僅可進行讀出的儲 存媒體、隨機存取記憶體（Random Access Me_y= RAM } 之類的揮發性記憶體、或該些的組合者。 再者，圖1中的目標變數分析部u、波形處理部12、 說明變數分析部13、模型生成部14及樣品分析部15既可 藉由^用的硬體而實現’另外，亦可藉由記龍及微處理 器而實現。另外，触各部亦可包含記紐財央處理器 (Central Processing Unit ’ CPU )’藉由將用以實現各部的 功能的程式載入至記憶體中來執行而實現其功能。 另外，將輸入裝置（未圖示）等作為周邊機器而連接 於利用该共聚合物評價方法進行共聚合物的評價的共聚合 物》平彳貝裝置上。此處，所謂輸入裝置，是指鍵盤、滑鼠等 輸入設備。所謂顯示部17，是指陰極射線管（Cath〇deRay Tube ’ CRT)或液晶顯示裝置等。 另外，將用以實現圖1中的目標變數分析部n、波形 處理部12、說明變數分析部13、模型生成部14及樣品分 析部15的功能的程式記錄於電腦可讀取的記錄媒體中使 電腦系統讀入、執行記錄於該記錄媒體中的程式，藉此亦 可進行二單元組分率的計算處理。再者，此處所述的「電 月白糸統」疋才曰包含作業糸統（〇perating SyStem，〇s )或周 邊機器等硬體者。 另外’若為利用全球資訊網（w〇rld wide Web，WWW) 系統的隋況，則「電腦糸統」亦包含首頁（h〇mepage )提 127 201222146 供％境（或顯示環境）。 另外，所謂「電腦可讀取的記錄媒體」 光碟、唯獨記憶體（Read 0nly Mem〇ry，R〇日二、、磁 内置於電腦系統中的硬碟等儲存裝置 而，所谓「電腦可讀取的記錄媒體」，/罝遣 暴狀，於短時_減_持程式者，It is compared with the total value of the obtained three-unit component ratio, and whether the characteristics of the household = the copolymer are suitable for the characteristics of the anti-composition. That is, the control unit 18 is suitable for the preparation of the anti-residue composition in the case where the total value of the obtained triad component ratio is less than the tri-unit component ratio (four), at the obtained three-unit composition ratio. When the total value exceeds the three-site fractional limit value, it is determined that the preparation of the anti-(four) composition is not suitable, and the determination result is displayed on the display unit 17 for each polymer. &lt; Using the resist composition prepared as described above, a resist pattern is formed on a substrate, for example, a semiconductor substrate, whereby fine processing precision corresponding to the fine pattern of the exposure mask can be achieved. That is, it is possible to manufacture a substrate on which a pattern is formed on a substrate to be processed, which includes a step of applying a resist composition on a substrate to be processed, a step of exposing with light having a wavelength of 250 nm or less, and a step of exposing the substrate to a substrate to be processed, and The step of developing with a developing solution. Here, the wavelength of 250 nm or less is set to use KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), EUV (Extreme) in the resist composition of the present embodiment. 125 201222146 On the excimer laser of light (wavelength: 13 nm), it corresponds to the lithography process of = irradiated light. The composition of the anti-surname agent in the present embodiment is preferably an anti-contact agent composition which is preferable for the short-wavelength of the irradiation light and the refinement of the pattern, and the acid-desorbable group is desorbed by the action of an acid. So-called chemically amplified anti-side compositions of soluble polymers and photoacid generators are tested. a material f T copolymerized composition of the present embodiment is prepared by copolymerization of 1 unit component_================================================================== Below the ear %, less than the molar %, more preferably set to i3 β and then the early morning 兀 component rate limit. Γ : ! = = = = = = = = = = = = = = 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体Into (construction:) single ^! =; 丨: the monomer polymer is sent out for evaluation 昧 (4) )) % of the lithography process using the common unit component rate t: in the monomer unit three for the determination It is a preparation for the composition of the lithography process. Preferably, the storage unit 16 is set to include a hard disk device or a magneto-optical disk device, and the ratio of the component rate of the three components is 15% or less, more preferably 13% by mole or less. 126 201222146 H-UZO〇pif Non-volatile memory such as flash memory, CD-ROM (10) Disc Read Only Memory 'CD-ROM, etc. Only storage media and random access memory (Random Access) Volatile memory such as Me_y = RAM }, or a combination of these. Further, the target variable analysis unit u, the waveform processing unit 12, the explanatory variable analysis unit 13, the model generation unit 14, and the sample analysis in Fig. 1 The part 15 can be realized by the hardware used by the device. Alternatively, it can also be realized by the recorder and the microprocessor. In addition, the touch unit can also include the central processing unit 'CPU'. The function is realized by loading a program for realizing the functions of the respective units into the memory. Further, an input device (not shown) or the like is connected as a peripheral device to the copolymerization method using the copolymer evaluation method. Copolymer of the evaluation of matter Here, the input device refers to an input device such as a keyboard or a mouse. The display unit 17 is a cathode ray tube (Cath〇 deRay Tube 'CRT), a liquid crystal display device, or the like. The program for realizing the functions of the target variable analysis unit n, the waveform processing unit 12, the variable analysis unit 13, the model generation unit 14, and the sample analysis unit 15 in FIG. 1 is recorded in a computer-readable recording medium to read the computer system. The program recorded in the recording medium is executed, whereby the calculation of the two-unit component rate can also be performed. Furthermore, the "Electric Moonlight System" described herein includes the operating system (〇perating SyStem) , 〇s ) or peripheral devices and other hardware. In addition, if you use the World Wide Web (WWW) system, the "Computer System" also contains the home page (h〇mepage) 127 201222146 For the environment (or the display environment). In addition, the so-called "computer-readable recording media" CD-ROM, only memory (Read 0nly Mem〇ry, R〇日二, magnetic hard disk built into the computer system Storage device However, the so-called "computer-readable recording media", / 暴 暴 ,, in a short time _ minus _ programmer,

祠服器（_〇或客戶端（client)的電腦系統内部的揮 發性記憶體般，將程式保持固定時間者。另外，上述程 可為用以實現上述功能的-部分者，進而亦可為可藉二 已記錄於電腦系統中的程式的組合而實現上述功能^。〃 以下，對關於本實施形態的微影製程用共聚合物的製 造方法的例進行說明。 〈參考例B-1:後步驟中所使用的溶液^^的組成的設 計&gt;The server (such as _〇 or the client's computer system's internal volatility memory, keeps the program for a fixed period of time. In addition, the above process can be used to achieve the above-mentioned functions, and further can be borrowed The above-described functions are realized by a combination of the programs recorded in the computer system. The following describes an example of a method for producing a lithographic process copolymer according to the present embodiment. <Reference Example B-1: Post-step Design of the composition of the solution ^^ used in the process&gt;

本例是求出使由上述式（m-Ι )、上述式（m_2)、上述 式（m-3)所表示的單體m-l、單體m-2、單體m_3進行聚 合’而製造目才示組成為m-1 . in-2 . m-3 = 40 : 40 : 20 (莫 耳％)’重量平均分子量的目標值為1〇,〇〇〇的聚合物時的 Uc的組成的例。 本例中所使用的聚合起始劑是二曱基_2,2，-偶氮雙異 丁酸酯（和光純藥工業公司製造，V601 (商品名聚合 溫度設為80°C。 於氮氣環境下，將乳酸乙酯67.8份加入至具備氮氣導 128 201222146 HUZOOpif 入口、攪拌機、冷凝器、滴液漏斗、及溫度計的燒瓶（反 應器）中。將燒瓶放入至水浴中，一邊對燒瓶内進行擾拌 一邊將水浴的溫度提高至80t。In this example, the monomer ml, the monomer m-2, and the monomer m_3 represented by the above formula (m-Ι), the above formula (m_2), and the above formula (m-3) are obtained by polymerization. The composition is m-1. in-2 . m-3 = 40 : 40 : 20 (mole %) 'The target value of the weight average molecular weight is 1 〇, and the composition of Uc in the case of ruthenium polymer . The polymerization initiator used in this example is dimercapto 2,2,-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., V601 (trade name polymerization temperature is set to 80 ° C. in a nitrogen atmosphere). Next, 67.8 parts of ethyl lactate was added to a flask (reactor) equipped with a nitrogen gas guide of 128 201222146 HUZOOpif inlet, a stirrer, a condenser, a dropping funnel, and a thermometer. The flask was placed in a water bath while the inside of the flask was placed. The temperature of the water bath was raised to 80t while disturbing.

其後’自滴液漏斗歷時4小時以固定的滴加速度向燒 瓶内滴加含有下述的單體混合物、溶劑、及聚合起始劑的 滴加溶液三進而將80。〇的溫度保持3小時。自滴加溶液的 滴加開始算起7小時後，冷卻至室溫為止而使反應停止。 單體m-1 28.56份（4〇莫耳％)、 單體m-2 32.93份（4〇莫耳％)、 單體m-3 19.82份（2〇莫耳％)、 乳酸乙酯122.0份、 一甲基'2,2,偶氮雙異丁酸酯2.415份（相對於單體的 總供給量為2.5莫耳％)。 自上述滴加溶液的滴加開始算起〇 5小時、1小時、2 小時、3,小時、4小時、5小時、6小時、7小時後，分別 ^樣燒瓶内的聚合反應溶液G.5 g ’並分別進行單體瓜巧〜Thereafter, the dropping solution containing the monomer mixture, the solvent, and the polymerization initiator described below was added dropwise from the dropping funnel to the flask at a fixed dropping rate for 4 hours to further 80. The temperature of the crucible was kept for 3 hours. Seven hours after the start of the dropwise addition of the dropwise addition solution, the reaction was stopped by cooling to room temperature. Monomer m-1 28.56 parts (4 〇 mol%), monomer m-2 32.93 parts (4 〇 mol%), monomer m-3 19.82 parts (2 〇 mol%), ethyl lactate 122.0 parts Methyl '2,2, azobisisobutyrate 2.415 parts (2.5 mol% relative to the total monomer supply). The polymerization reaction solution G.5 in the flask was respectively taken from the start of the dropwise addition of the above dropwise addition solution for 5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, and 7 hours. g 'and separately carry the monomer melon ~

單體m 2的&amp;量。藉此可知各採樣時殘存於燒瓶内的各單 體的質里。其結果’例如自滴加開始算起 時後的結果如表8所示。 JThe amount of monomer m 2 &amp; From this, it was found that the mass of each of the monomers remaining in the flask at the time of sampling was observed. The results are as shown in Table 8, for example, from the start of the dropwise addition. J

[表8] 單體 m-l (Μχ) &quot; —^±登後（質量份） 3小時後（質詈份1 單體 m-2 _____4.UU 7 0A 4.00 n nc -- 單體 m-3 &quot; ----- / .ZH· 2.89 7.75 2.90 129 201222146 繼而，使用各單體的分子量，換算成各 燒瓶内的各單體的莫耳分率（相#於他：吻：^存於 結果如自滴加開始算起2小時後舆3小時後的 [表9][Table 8] Monomer ml (Μχ) &quot; —^± After (parts by mass) 3 hours later (mass 11 monomer m-2 _____4.UU 7 0A 4.00 n nc -- monomer m-3 &quot ;-- / .ZH· 2.89 7.75 2.90 129 201222146 Then, using the molecular weight of each monomer, the molar fraction of each monomer in each flask is converted (phase: he: kiss: ^ in the result) For example, 2 hours after the start of the drip, 舆 3 hours later [Table 9]

的各單二曰f 時固定速度向燒瓶内供給 的各早體的合計質量，並自該 ϋ ft的各單體的質量，藉此針對各 單體之中轉化成聚合物者的f量。， 與採樣時之; =耳:::r:r各採樣時與採樣 為止的期間、自(反應時間)自 中的單體單元“有比im·:分別生成的聚合物 比）Uy : Pz 有時亦稱為聚合物組成 將所獲传的結果示於圖一 段(採樣時與採樣時之間)的4:==各反應時 圖5 一反應時間為4:;:==二： 130 201222146 HU^OOpif 加開始算起3小時後〜4小時後所生成的聚合物的資料（以 下相同）。 如圖5的結果所示，聚合物組成比（Px : Py : Pz)最 接近作為目標組成的40 : 40 : 20者是自滴加開始算起2 小時後〜3小時後所生成的聚合物，為Px:Py:Pz = 41.05 : 38.47 : 20.48。 若使用該值與自滴加開始算起的經過時間為2小時後 的 Mx: My: Mz 的值（表 9 )，根據 Fx = Px/Mx、Fy = Py/My、 Fz = Pz/Mz而求出因數Fx、因數Fy、因數Fz，則變成Fx = 1.27、Fy= 0.76、Fz= 1.22。此時，根據 Fy&lt;Fz&lt;Fx， 將Fy替換為0。 使用該因數的值與目標組成求出Uc的組成x〇 : y〇 : Z〇 0 x〇 = 4〇xFx/ ( 4〇xFx +4〇xFy + 2〇xFz) =4〇χ1.27/(4〇χ1.27 +4〇χ〇 + 2〇χ1.22) = 67.6 莫耳％。 y〇 = 4〇xFy/ (4〇xFx +4〇xFy + 2〇xFz) = 4〇χ〇/ (4〇χ1.27 + 4〇χ〇 + 2〇χ1.22) =0 莫耳％。 z〇=2〇xFz/ (4〇xFx+4〇xFy + 2〇xFz) =2〇χ1·22/(4〇χ1·27 +4〇x〇 +20x1.22) = 32.4 莫耳％。 &lt;實例B-l&gt; 131 201222146 -ruz.oopii 本例中’於事先將溶液Sa(於本說明書中，有時僅稱 為Sa。Tb、Uc亦相同。）供給至反應器内，然後滴加Tb 及聚合起始劑溶液的主步驟後，設置滴加Uc的後步驟。 使用參考例B_1中所求出的Uc的組成。所使用的單 體的種類、聚合起始劑的種類、聚合溫度、聚合物的目標 組成、及重量平均分子量的目標值與參考例B-1相同。將 Sa的單體組成設為與以使用上述因數的方法所設計的第1 組成相同，將Tb的單體組成設為與目標組成相同。 [Sa的第1組成的設計] 使用參考例B-1中所求出的因數的值（Fx=1 27、Fy = 0·76、Fz=1.22)與目標組成求出第i組成，將其作為 Sa的單體組成。 x〇〇 = 40/Fx = 40/1.27=約 31.3 莫耳％。 y〇o —40/Fy = 40/0.76=約 52.4 莫耳％。 z〇〇 = 20/Fz = 20/1.22=約 16.3 莫耳％。 於氮氣環境下，將下述的Sa (S1)加入至具備氮氣導 入口、授拌機、冷凝H、2個滴液漏斗、及溫度計的燒瓶 中。將燒瓶放入至水浴中，一邊對燒瓶内進行攪拌一邊將 水浴的溫度提高至80。(：。 其後，自另一個滴液漏斗同時開始下述的^^^丁丨）與 聚合起始劑溶液的供給，歷時4小時將Tb滴加至燒瓶内， 歷時20分鐘將聚合起始劑溶液滴加至燒瓶内。進而，自剛 201222146 H-UZOOpif 結束Tb的供給之後，歷時1小時滴加下述Uc中的80質 量％ (U1)，然後歷時1小時滴加剩餘的20質量％ (U2)， 進而，將80°C的溫度保持1小時。自Tb的滴加開始算起 7小時後，冷卻至室溫為止而使反應停止。 於本例中，Uc所含有的單體的合計量為總單體供給量 的2.15質量％。 (Sa) 單體m-1 3.99份（31.3莫耳％)、 單體m-2 7.68份（52·4莫耳％)、 單體m-3 2.88份（16.3莫耳％)、 乳酸乙酯99.3份。 (Tb) 單體m-1 24.03份（40莫耳％)、 單體m-2 27.71份（40莫耳％)、 單體m-3 16.68份（20莫耳％)、 乳酸乙酯101.8份、 二曱基-2,2'-偶氮雙異丁酸酯蚤0.690份（相對於Sa 及Tb中的單體的合計量為0.7莫耳％)。 (聚合起始劑溶液） 乳酸乙酯2.0份、 二甲基-2,2’-偶氮雙異丁酸酯1.280份（相對於Sa及 Tb中的單體的合計量為1.3莫耳％ )。 (Uc) 單體m-1 1.09份（67_6莫耳％)、 133 201222146 單體m-3 0.73份（32 4莫耳％)、 乳酸乙酯34.5份、 一甲基·2,2’-偶氣雙異丁酸酯0.054份（相對於xjc中 的單體的合計量為2 5莫耳％)。 、以與參考例W相同的程序，求出各反應時間内所生 成的聚合物巾的單體單元的含有比率（聚合物組成比）。將 其結果示於圖6。 右對圖5與圖6的結果進行比較，則參考例B-1(圖5) :’於主步驟的初期所生成的聚合物的聚合物組成比與目 標組成的絲大。另外，關於自作為主步驟的結束（滴加 液的U)時的反應時間4小時至作為保持步驟的結束時 的反應時間7小時之間所生成的聚合物，聚合物組成比與 目才示組成的差隨時間經過而變大。 相對於此，實例B_2 (圖6)於主步驟中使用利用上述 因數設計單體組成的Sa、及目標組成的Tb，且於主步驟 的結束（Tb的滴加結束）後設置供給合計2小時的^^的 後步驟，藉此於主步驟中，自剛開始聚合反應之後生成與 目標組成大致相同組成的聚合物分子，且該狀態持續於 主步驟的結束（反應時間4小時）後，聚合物組成比亦顯 示與目標組成非常接近的值，由反應時間所引起的組 的偏差得到改善。 * [聚合物的精製] 於經過反應時間7小時後，冷卻至室溫為止而使反應 停止，一邊攪拌一邊將燒瓶内的聚合反應溶液滴加至約&amp; 134 201222146 ^uzoopif 倍量的曱醇及水的混合溶劑（曱醇/水= 80/20容量比）中， 獲得白色的析出物（聚合物pl)的沈澱。將沈澱濾除，再 次投入至與上述相同量的甲醇及水的混合溶劑（曱醇/水= 90/10容量比）中，一邊攪拌一邊進行沈澱的清洗。然後’ 將清洗後的沈澱濾除，獲得聚合物濕粉160 g。於減壓下 以40°C對該聚合物濕粉中的1〇 g進行約40小時乾燥。針 對所獲得的聚合物P1求出Mw、Mw/Mn，並進行溶解性Each of the individual enthalpy f is a fixed mass of the respective precursors supplied to the flask at a fixed rate, and the mass of each monomer from the ft, thereby the amount of f converted into a polymer among the monomers. , and when sampling; = ear:::r:r The period from the sampling to the sampling period, from the (reaction time) from the monomer unit "has the ratio of the polymer produced by im:: separately" Uy : Pz Sometimes referred to as polymer composition, the results obtained are shown in the first section of the figure (between sampling and sampling). 4:== each reaction time Figure 5 One reaction time is 4:;:==two: 130 201222146 HU^OOpif Add the data of the polymer generated after 3 hours to 4 hours (the same applies hereinafter). As shown in the results of Fig. 5, the polymer composition ratio (Px: Py: Pz) is the closest to the target. The composition of 40:40:20 is the polymer formed after 2 hours from the start of the dropwise addition, and is Px:Py:Pz = 41.05: 38.47: 20.48. If this value is used and the self-drip is started The elapsed time is the value of Mx: My: Mz after 2 hours (Table 9), and the factor Fx, factor Fy, factor is obtained according to Fx = Px/Mx, Fy = Py/My, Fz = Pz/Mz Fz, then Fx = 1.27, Fy = 0.76, Fz = 1.22. At this time, according to Fy&lt;Fz&lt;Fx, replace Fy with 0. Use the value of this factor and the target composition to find the composition of Uc: 〇 : Z 0 x〇= 4〇xFx/ ( 4〇xFx +4〇xFy + 2〇xFz) =4〇χ1.27/(4〇χ1.27 +4〇χ〇+ 2〇χ1.22) = 67.6 Mohr %. y〇= 4〇xFy/ (4〇xFx +4〇xFy + 2〇xFz) = 4〇χ〇/ (4〇χ1.27 + 4〇χ〇+ 2〇χ1.22) =0 Moer %。z〇=2〇xFz/ (4〇xFx+4〇xFy + 2〇xFz) =2〇χ1·22/(4〇χ1·27 +4〇x〇+20x1.22) = 32.4 % &lt;Example B-l&gt; 131 201222146 -ruz.oopii In this example, the solution Sa (in the present specification, sometimes only referred to as Sa. Tb, Uc is also the same) is supplied to the reactor, and then After the main step of dropwise adding Tb and a polymerization initiator solution, a step of dropping Uc was provided. The composition of Uc determined in Reference Example B_1 was used. The type of monomer used, the type of polymerization initiator, The target values of the polymerization temperature, the target composition of the polymer, and the weight average molecular weight were the same as in Reference Example B-1. The monomer composition of Sa was set to be the same as the first composition designed by the method using the above factors, and Tb was The monomer composition is set to be the same as the target composition. [Design of the first composition of Sa] Using the reference example B-1 Factor value (Fx = 1 27, Fy = 0 · 76, Fz = 1.22) to obtain the target composition and the composition of the i-th, which is composed of, as monomer Sa. X〇〇 = 40/Fx = 40/1.27 = approx. 31.3 mol %. Y〇o —40/Fy = 40/0.76=about 52.4% of the mole. Z〇〇 = 20/Fz = 20/1.22 = about 16.3 mole %. The following Sa (S1) was placed in a flask equipped with a nitrogen gas inlet, a mixer, a condensed H, two dropping funnels, and a thermometer under a nitrogen atmosphere. The flask was placed in a water bath, and the temperature of the water bath was raised to 80 while stirring the inside of the flask. (:. Thereafter, the supply of the polymerization initiator solution was started simultaneously from another dropping funnel), and Tb was added dropwise to the flask over 4 hours, and the polymerization was started for 20 minutes. The solution was added dropwise to the flask. Further, after the supply of Tb was completed from 201222146 H-UZOOpif, 80% by mass (U1) of the following Uc was added dropwise over one hour, and then the remaining 20% by mass (U2) was added dropwise over one hour, and further, 80 was added. The temperature of °C was maintained for 1 hour. Seven hours after the start of the dropwise addition of Tb, the reaction was stopped by cooling to room temperature. In the present example, the total amount of the monomers contained in Uc was 2.15 mass% of the total monomer supply amount. (Sa) monomer m-1 3.99 parts (31.3 mol%), monomer m-2 7.68 parts (52·4 mol%), monomer m-3 2.88 parts (16.3 mol%), ethyl lactate 99.3 servings. (Tb) monomer m-1 24.03 parts (40 mol%), monomer m-2 27.71 parts (40 mol%), monomer m-3 16.68 parts (20 mol%), ethyl lactate 101.8 parts 0.690 parts of dimercapto-2,2'-azobisisobutyrate ruthenium (0.7 mol% relative to the total amount of monomers in Sa and Tb). (Polymerization initiator solution) 2.0 parts of ethyl lactate and 1.280 parts of dimethyl-2,2'-azobisisobutyrate (1.3 mol% relative to the total amount of monomers in Sa and Tb) . (Uc) Monomer m-1 1.09 parts (67_6 mol%), 133 201222146 Monomer m-3 0.73 parts (32 4 mol%), ethyl lactate 34.5 parts, monomethyl-2,2'-even Gaso-isoisobutyrate 0.054 parts (compared to the total amount of monomers in xjc is 25 mol%). The content ratio (polymer composition ratio) of the monomer unit of the polymer towel produced in each reaction time was determined by the same procedure as in Reference Example W. The result is shown in Fig. 6. On the right, comparing the results of Fig. 5 with Fig. 6, reference example B-1 (Fig. 5): The polymer composition ratio of the polymer formed at the beginning of the main step is larger than that of the target composition. In addition, about the polymer formed from the reaction time of 4 hours from the end of the main step (U of the dropping liquid) to the reaction time of 7 hours as the end of the holding step, the polymer composition ratio and the purpose are shown. The difference in composition becomes larger as time passes. On the other hand, in the main step, the example B_2 (FIG. 6) uses the composition of the above-described factors to design the composition of the monomer Sa and the Tb of the target composition, and sets the total supply for 2 hours after the end of the main step (the end of the dropwise addition of Tb). a subsequent step of the ^^, whereby in the main step, a polymer molecule having a composition substantially the same as the target composition is formed immediately after the polymerization reaction, and the state continues after the end of the main step (reaction time 4 hours), and the polymerization is carried out. The composition ratio also shows a value very close to the target composition, and the deviation of the group caused by the reaction time is improved. * [Refinement of the polymer] After the reaction time was 7 hours, the reaction was stopped after cooling to room temperature, and the polymerization reaction solution in the flask was added dropwise to the mixture of propylene at about &lt; 134 201222146 ^uzoopif In a mixed solvent of water (sterol/water = 80/20 capacity ratio), a precipitate of a white precipitate (polymer pl) was obtained. The precipitate was filtered off, and the mixture was again added to the same amount of a mixed solvent of methanol and water (sterol/water = 90/10 capacity ratio), and the precipitate was washed while stirring. Then, the washed precipitate was filtered off to obtain a polymer wet powder of 160 g. The 〇g in the polymer wet powder was dried at 40 ° C for about 40 hours under reduced pressure. Mw, Mw/Mn were determined for the obtained polymer P1, and solubility was measured.

的評價。將結果示於表20。 [抗蝕劑組成物的製造] 將上述聚合物濕粉的剩餘部分投入至PGMEA 880 g 中，使其完全溶解而製成聚合物溶液後，使該聚合物溶液 於孔徑為0.04 μιη的尼龍製過濾器（日本Pall公司製造， P-NYLON N66FILTER0.04M (商品名））中通過，而對聚 合物溶液進行過瀘。 於減壓下對所獲得的聚合物溶液進行加熱來餾去曱醇 及水，進而餾去PGMEA，獲得聚合物的濃度為25質量％ 的t合物P1溶液。此時，最高到達真空度為〇 7 ，最 高溶液溫度為651，餾去時間為 8小時。 一，所^得的聚合物P1溶液400份、作為光酸產生劑 的三„三氟甲燒雜鹽2份、以及作為溶劑的pgmea 為12.5 f 4%的方式混合而製成均句溶液 劑組成物01卜@的薄膜過濾器進行過濾，獲得抗勒 價感光度。將's=劑組成物’利用上述方法評 135 201222146 &lt;比較例B-l&gt; 於實例B-1中，將後步驟中滴加的Uc中所含有的單 體的合計量變更為總單體供給量的14.9質量％。 即，除將Sa〜Uc及聚合起始劑溶液的組成分別如以 下般變更以外，與實例B-1同様地進行。 (Sa) 單體m-1 3.99份（31.3莫耳％)、 單體m-2 7.68份（52.4莫耳％)、 單體m-3 2·88份（16.3莫耳％)、 乳酸乙酯99.3份。 (Tb) 單體m-1 24.03份（40莫耳％)、 單體m-2 27.71份（40莫耳％)、 單體m-3 16.68份（20莫耳％)、 乳酸乙酯101.8份、 二曱基-2,2’-偶氮雙異丁酸酯0.690份（相對於Sa及 Tb中的單體的合計量為0.7莫耳％)。 (聚合起始劑溶液） 乳酸乙酯2.0份、 二曱基-2,2’-偶氮雙異丁酸酯1.280份（相對於Sa及 Tb中的單體的合計量為1.3莫耳％ )。 (Uc) 單體 m-1 8.72 份（67.6 莫耳·％)、 單體m-3 5.84份（32.4莫耳％)、 201222146 乳酸乙酯34.5份、 二曱基·2,2’·偶氮雙異·^旨Q 4 的單體的合計量為2.5莫耳％)。 t於Uc中 以與參考例Μ相同的程序，求出各反應時間内所生 成的聚合物中的單體單摘含右錢川内所生 其結果示於圖7。 3有叫（聚合她成比）。將evaluation of. The results are shown in Table 20. [Production of Resist Composition] The remainder of the above polymer wet powder was placed in PGMEA 880 g to be completely dissolved to prepare a polymer solution, and the polymer solution was made of nylon having a pore size of 0.04 μm. The filter (manufactured by Pall Corporation, P-NYLON N66FILTER 0.04M (trade name)) was passed through, and the polymer solution was subjected to ruthenium. The obtained polymer solution was heated under reduced pressure to distill off methanol and water, and then PGMEA was distilled off to obtain a t compound P1 solution having a polymer concentration of 25% by mass. At this time, the highest reached vacuum was 〇 7 , the highest solution temperature was 651, and the distillation time was 8 hours. First, 400 parts of the obtained polymer P1 solution, 2 parts of tris-trifluoromethane salt as a photoacid generator, and pgmea as a solvent are 12.5 f 4% to prepare a homogenous solution. The membrane filter of composition 01 was filtered to obtain anti-price sensitivity. 's = agent composition' was evaluated by the above method 135 201222146 &lt;Comparative Example B-1&gt; In Example B-1, the latter step The total amount of the monomers contained in the Uc added dropwise was changed to 14.9% by mass of the total monomer supply amount. That is, the composition of Sa~Uc and the polymerization initiator solution was changed as follows, and examples were given. B-1 was carried out in the same manner. (Sa) Monomer m-1 3.99 parts (31.3 mol%), monomer m-2 7.68 parts (52.4 mol%), monomer m-3 2.88 parts (16.3 mo Ear %), 99.3 parts of ethyl lactate. (Tb) Monomer m-1 24.03 parts (40 mol%), monomer m-2 27.71 parts (40 mol%), monomer m-3 16.68 parts (20 Mol%), 101.8 parts of ethyl lactate, 0.690 parts of dimercapto-2,2'-azobisisobutyrate (0.7 mol% relative to the total amount of monomers in Sa and Tb). Polymerization initiator solution) lactic acid 2.0 parts of ester, 1.280 parts of dimercapto-2,2'-azobisisobutyrate (1.3 mol% relative to the total amount of monomers in Sa and Tb). (Uc) Monomer m-1 8.72 parts (67.6 mol·%), monomer m-3 5.84 parts (32.4 mol%), 201222146 ethyl lactate 34.5 parts, dimercapto 2,2'·azodiiso^^^ Q 4 The total amount of the monomers was 2.5 mol%.) In Uc, the same procedure as in the reference example was used to determine the results of the monomer extracts in the polymer produced in each reaction time. Shown in Figure 7. 3 is called (aggregate her into comparison).

與^例B 1 (圖6)相比，比較例u (圖7)因總單 體供給量之快後倾所供給的賴的關過多，故^步 Γϊ、?ί (if 1 夺間4小時)後所生成的聚合物的聚合物 =匕==的差較大，另外，因反應時間而導致聚 &amp;物組成的偏差較大4對所獲得的聚合物求出Μ*， Mw/Mn ’並進行溶解性的評價。將結果示於表2〇。 &lt;參考例Β·2:後㈣帽❹恤液⑸的組成的設 吕十&gt; 本例是求出使由上述式（m_4)、上述式（m_5)、上述 式（m-3)所表示的單體m_4、單體办5、單體m 3進行聚 合’而製造目標組成為m_4: m_5 : m_3==35 : 35 : 3〇 (莫 耳/〇)、重里平均分子量的目標值為7，_的聚合物時的 Uc的組成的例。 t合起始劑使用與參考例相同的二甲基_2,2,_偶氮 雙異丁酸酯’聚合溫度設為8〇。〇。 於氮氣環境下，將乳酸乙酯31 7份與pGMEA31 7份 加入至具備氮氣導入口、攪拌機、冷凝器、滴液漏斗、及 皿度计的燒瓶中。將燒瓶放入至水浴中，一邊對燒瓶内進 137 201222146 行邊將切的溫度提高至80。〇 ,其後丄自滴液漏斗歷時4小時以固定的滴加速度向燒 加3有下述的單體混合物、溶劑、及聚合起始劑的 進而將8〇。〇的溫度保持3小時。自滴加溶液的 '起7小時後’冷卻至室溫為止而使反應停止。 早體 m-4 20.83 份（35 莫耳。/〇)、 ，體 m_5 30.38 份（35 莫耳％)、 單體 m-3 24.78 份（30 莫耳。/〇)、 乳酸乙酯57.0份、 ' PGMEA 57.0 份、Compared with the case B 1 (Fig. 6), the comparative example u (Fig. 7) has too much supply due to the fast back tilt of the total monomer supply amount, so ^step Γϊ, ?ί (if 1 夺间4 After the hour), the polymer of the polymer produced = 匕 == has a large difference, and the variation of the composition of the poly &amp; composition is large due to the reaction time. 4 The obtained polymer is obtained as Μ*, Mw/ Mn 'and evaluation of solubility. The results are shown in Table 2〇. &lt;Reference example 22: The composition of the composition of the posterior (four) cap-tie liquid (5) is set as follows: This example is obtained by the above formula (m_4), the above formula (m_5), and the above formula (m-3). The indicated monomer m_4, monomer 5, and monomer m 3 are polymerized' and the target composition is m_4: m_5 : m_3 == 35 : 35 : 3 〇 (mole / 〇), the target value of the average molecular weight of the weight An example of the composition of Uc when the polymer is 7,_. The t-starting agent used was the same dimethyl-2,2,-azobisisobutyrate as the reference example, and the polymerization temperature was set to 8 Torr. Hey. In a nitrogen atmosphere, 31 parts of ethyl lactate and 7 parts of pGMEA31 were placed in a flask equipped with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, and a potentiometer. The flask was placed in a water bath, and the temperature of the cut was raised to 80 while the inside of the flask was 137 201222146. Then, the crucible funnel was further heated from the dropping funnel over a period of 4 hours at a fixed dropping rate to the following monomer mixture, solvent, and polymerization initiator. The temperature of the crucible was kept for 3 hours. The reaction was stopped after cooling to room temperature from 'after 7 hours from the dropwise addition of the solution. Early body m-4 20.83 parts (35 moles / 〇), body m_5 30.38 parts (35 mole%), monomer m-3 24.78 parts (30 moles / 〇), ethyl lactate 57.0 parts, ' PGMEA 57.0 copies,

小時起。.5小時、1小時、: 採樣燒瓶内的聚合反應溶液。:5二^ ^From the hour. .5 hours, 1 hour,: The polymerization solution in the sample flask was sampled. :5 2^ ^

體的質量。其結果，例如自燒瓶内的各單 時後的結果如表10所示。h始异起3小時後與M、 [表 10]The quality of the body. As a result, for example, the results after each single time in the flask are shown in Table 10. h starts after 3 hours with M, [Table 10]

換异成各採樣時殘存於 3'了 單體 m-4(Mx) 單體m-5 (My) 單體 m-3 (Mz) 繼而，使用各單體的分子量， 138 201222146 ^uz-oopif 燒瓶内的各單體的莫耳分率（相當於Mx : My : Mz)。 其結果，例如自滴加開始算起3小時後與4小時後的 結果如表11所示。Divided into each sample when remaining in 3' monomer m-4 (Mx) monomer m-5 (My) monomer m-3 (Mz), then, using the molecular weight of each monomer, 138 201222146 ^uz-oopif The molar fraction of each monomer in the flask (corresponding to Mx: My : Mz). As a result, for example, the results after 3 hours from the start of the dropwise addition and the results after 4 hours are shown in Table 11.

139 201222146 [表η] 3小時後（莫耳％) 4小時後（莫耳％) 單體 m-4 (Mx) 23.35 22.45 單體 m-5 (My) 57.35 58.88 單體 m-3 (Mz) 19.30 18.67 以與參考例Β-l相同的方式，求出各反應時段内所生 成的聚合物中的單體單元的含有比率。將其結果示於圖8。 如圖8的結果所示，聚合物組成比（Px : Py : Pz)最 接近作為目標組成的35 : 35 : 30者是自滴加開始算起3 小時後〜4小時後所生成的聚合物，為Px: Py: Pz= 37.36 : 32.61 : 28.95。 若使用該值與自滴加開始算起的經過時間為3小時後 的 Mx : My : Mz 的值（表 11 )，根據 Fx = Px/Mx、Fy = Py/My、Fz = Pz/Mz而求出因數Fx、因數Fy、因數Fz，則 變成 1.60、Fy=0.60、Fz= 1.50。此時，牙艮據 Fy&lt;Fz &lt;Fx，將Fy替換為0。 使用該因數的值與目標組成求出Uc的組成x〇 : y〇 : x〇=35xFx/ ( 35&gt;&lt;Fx +35&gt;&lt;Fy + 3〇xFz) =35x1.60/(35x1.60 +35χ〇 +30x1.50) = 55.4 莫耳％。 y〇=35&gt;&lt;Fy/ (35&gt;&lt;Fx+35xFy + 3〇xFz) = 35x0/ (35x1.60 + 35x0 + 30x1.50) =0 莫耳 ％。 140 201222146 4UZ88pif z〇=3〇xFz/ (35xFx+35xFy-h3〇xFz) = 30xl.50/(35xl 6〇 + 35x〇 + 3〇xl 5〇)=44 6 莫耳％。 &lt;實例B-2&gt; 本例中’於事先將溶液Sa供給至反應器内，然後滴加 Tb及聚合起始劑溶液的主步驟後，設置滴加Uc的後步驟。 使用參考例B-2中所求出的Uc的組成。所使用的單 體的種類、聚合起始劑的種類 '聚合溫度、聚合物的目標 組成、及重量平均分子量的目標值與參考例B_2相同。將 Sa的單體組成設為與以使用上述因數的方法所設計的第1 組成相同’將Tb的單體組成設為與目標組成相同。 [Sa的第1組成的設計] 使用參考例B-2中所求出的因數的值（px= 1 60、Fy = 0.60、Fz= 1.50)與目標組成求出第i組成，將其作為 Sa的單體組成。 x〇〇=35/Fx = 35/1.60=約 21.8 莫耳％。 5^〇〇=35/卩丫=35/0.60=約58.2莫耳〇/0。 z00 = 30/Fz = 30/1.50=約 20.0 莫耳％。 於氮氣環境下’將下述的Sa (S1)加入至具備氮氣導 入口、攪拌機、冷凝器、2個滴液漏斗、及溫度計的燒瓶 中。將燒瓶放入至水浴中，一邊對燒瓶内進行擾拌一邊將 141 201222146 nuz-oopii 水浴的溫度提高至。 聚4=:::=: =開始下_(T1)與 = =加=139 201222146 [Table η] After 3 hours (% by mole) 4 hours later (% by mole) Monomer m-4 (Mx) 23.35 22.45 Monomer m-5 (My) 57.35 58.88 Monomer m-3 (Mz) 19.30 18.67 The content ratio of the monomer unit in the polymer formed in each reaction period was determined in the same manner as in the reference example -1. The result is shown in Fig. 8. As shown in the results of Fig. 8, the polymer composition ratio (Px: Py: Pz) is the closest to the target composition of 35:35:30, which is the polymer formed after 3 hours from the start of the dropwise addition. , Px: Py: Pz = 37.36: 32.61: 28.95. If this value is used, the value of Mx : My : Mz after 3 hours elapsed from the start of the titration (Table 11), according to Fx = Px/Mx, Fy = Py/My, Fz = Pz/Mz When the factor Fx, the factor Fy, and the factor Fz are obtained, it becomes 1.60, Fy=0.60, and Fz=1.50. At this time, the gum is replaced with 0 according to Fy&lt;Fz &lt;Fx. Use the value of this factor and the target composition to find the composition of Uc x〇: y〇: x〇=35xFx/ ( 35&gt;&lt;Fx +35&gt;&lt;Fy + 3〇xFz) =35x1.60/(35x1.60 +35χ〇+30x1.50) = 55.4% of the mole. Y〇=35&gt;&lt;Fy/ (35&gt;&lt;Fx+35xFy + 3〇xFz) = 35x0/ (35x1.60 + 35x0 + 30x1.50) =0 Mo %. 140 201222146 4UZ88pif z〇=3〇xFz/ (35xFx+35xFy-h3〇xFz) = 30xl.50/(35xl 6〇 + 35x〇 + 3〇xl 5〇)=44 6 mole %. &lt;Example B-2&gt; In the present example, after the main step of supplying the solution Sa to the reactor in advance and then dropwise adding the Tb and the polymerization initiator solution, a subsequent step of dropping Uc was set. The composition of Uc found in Reference Example B-2 was used. The type of the monomer to be used and the type of the polymerization initiator "the polymerization temperature, the target composition of the polymer, and the target value of the weight average molecular weight are the same as those of Reference Example B_2. The monomer composition of Sa was set to be the same as the first composition designed by the method using the above factors. The monomer composition of Tb was set to be the same as the target composition. [Design of the first composition of Sa] Using the values of the factors obtained in Reference Example B-2 (px = 1 60, Fy = 0.60, Fz = 1.50) and the target composition, the ith composition is obtained, and this is taken as Sa. Monomer composition. X〇〇=35/Fx = 35/1.60=about 21.8 mole%. 5^〇〇=35/卩丫=35/0.60=about 58.2 moles/0. Z00 = 30/Fz = 30/1.50 = approx. 20.0 mol %. The following Sa (S1) was placed in a flask equipped with a nitrogen gas inlet, a stirrer, a condenser, two dropping funnels, and a thermometer under a nitrogen atmosphere. The flask was placed in a water bath, and the temperature of the 141 201222146 nuz-oopii water bath was raised while disturbing the inside of the flask. Poly 4=:::=:=Start _(T1) and ==Add=

I rT1的供給之後，歷時1小時滴加下述Uc中的則 里。’然後歷時1小時滴加剩餘的20質量％ (U2)， 進而將8〇t的溫度保持1小時。自Tb的滴加開始算起7 小時後’冷卻至室溫為止而使反應停止。 於本例中，Uc所含有的單體的合計量為總單體供給量 的2.68質量％。 (Sa) 單體 m-4 2.60 份（21.8 莫耳。/0)、 單體 m-5 10.13 份（58.2 莫耳％)、 單體m-3 3.30份（20.0莫耳％)、 乳酸乙醋46.5份、 PGMEA 46.5 份。After the supply of IrT1, the following Uc was added dropwise over one hour. Then, the remaining 20% by mass (U2) was added dropwise over 1 hour, and the temperature of 8 Torr was maintained for 1 hour. The reaction was stopped after cooling to room temperature 7 hours after the start of the dropwise addition of Tb. In the present example, the total amount of the monomers contained in Uc was 2.68 mass% of the total monomer supply amount. (Sa) monomer m-4 2.60 parts (21.8 mol./0), monomer m-5 10.13 parts (58.2 mol%), monomer m-3 3.30 parts (20.0 mol%), lactic acid ethyl acetate 46.5 parts, PGMEA 46.5 parts.

(Tb) 單體 m-4 16.66 份（35 莫耳。/〇)、 單體m-5 24.30份（35莫耳％ )、 單體m-3 24.00份（30莫耳％)、 乳酸乙酯26.9份、 PGMEA33.4 份、 二甲基-2,2'-偶氮雙異丁酸酯145〇份（相對於53及(Tb) Monomer m-4 16.66 parts (35 mol./〇), monomer m-5 24.30 parts (35 mol%), monomer m-3 24.00 parts (30 mol%), ethyl lactate 26.9 parts, 33.4 parts of PGMEA, 145 parts of dimethyl-2,2'-azobisisobutyrate (relative to 53 and

Tb中的單體的合計量為1.8莫耳％ )。 142 201222146 nv^oopif (聚合起始劑溶夜） 乳酸乙酯6.5份、 二曱基_2,2’-偶氣雙異丁酸醋2 m份（相對於％及 Tb中的單體的合計量為2 7莫耳％)。 (Uc) ' 單體m-4 1.00份（55 4莫耳％)、 單體m-3 1.12份（44 6莫耳％)、The total amount of monomers in Tb was 1.8 mol%). 142 201222146 nv^oopif (polymerization initiator dissolves night) 6.5 parts of ethyl lactate, 2 m parts of dimercapto 2,2'-oxybisisobutyric acid vinegar (relative to the total of monomers in % and Tb) The amount is 2 7 mol%). (Uc) 'Monomer m-4 1.00 part (55 4 mol%), monomer m-3 1.12 parts (44 6 mol%),

乳酸乙酯12.2份、 PGMEA 12.2 份、 二甲基-2,2'·偶氮雙異丁酸酯〇 11〇份（相 的單體的合計量為4.5莫耳％)。 ' 以與參考例B_1相同的程序，求出各反應時間内所生 成的聚合物中的單體單元的含有比率（聚合物組成比）。將 其結果示於圖9。 若對圖8與圖9的結果進行比較，則參考例B_2(圖8) 中，於主步驟的初期所生成的聚合物的聚合物組成比與目 標組成的差較大。另外，關於自作為主步驟的結束（滴加 液的結束）時的反應時間4小時至作為保持步驟的結束時 的反應時間7小時之間所生成的聚合物，聚合物組成比與 目標組成的差隨時間經過而變大。 ~ 相對於此，實例B-2 (圖9)於主步驟中使用利用上述 因數設計單體組成的Sa、及目標組成的Tb，且於主步驟 的結束（Tb的滴加結束）後設置供給合計2小時的Uc的 後步驟，藉此於主步驟中，自剛開始聚合反應之後生成與 143 201222146 目標組成大致相同組成的聚合物分子，且該狀態持續，於 主步驟的結束（反應時間4小時）後，聚合物組成比亦顯 示與目標組成非常接近的值，由反應時間所引起的組成比 的偏差得到改善。 [聚合物的精製] 除將實例B-1的聚合物的精製步驟中所使用的甲醇及 水的混合溶劑（曱醇/水= 80/20容量比）、及（曱醇/水== 90/10容量比）分別變更為甲醇及水的混合溶劑（甲醇/水 = 85/15容量比）、及（曱醇/水= 95/5容量比）以外，以與 實例B-1相同的方式，自經過了 7小時的反應時間的燒瓶 内的聚合反應溶液獲得聚合物P2。將聚合物P2的Mw、 Mw/Mn，溶解性評價的結果示於表20。 [抗蝕劑組成物的製造] 以與實例B-1相同的方式，製備含有聚合物P2的抗 蝕劑組成物，並評價感光度。將結果示於表20。 &lt;參考例B-3:後步驟中所使用的溶液Uc的組成的設 計&gt; 本例是求出使由上述式（m-Ι)、下述式（m-6)、下述 式（m-7)所表示的單體m-Ι、單體m-6、單體m-7進行聚 合，而製造目標組成為m-1 : m-6 : m-7 = 25 : 25 : 50 (莫 耳％)、重量平均分子量的目標值為10,000的聚合物時的 Uc的組成的例。 聚合起始劑使用與參考例B-1相同的二甲基-2,2'·偶氮 雙異丁酸酯，聚合溫度設為8(TC。 201222146 ^υ^οοριί12.2 parts of ethyl lactate, 12.2 parts of PGMEA, and 11 parts of dimethyl-2,2'-azobisisobutyrate oxime (the total amount of the monomers in the phase was 4.5 mol%). The content ratio (polymer composition ratio) of the monomer units in the polymer produced in each reaction time was determined in the same manner as in Reference Example B_1. The result is shown in Fig. 9. When the results of Fig. 8 and Fig. 9 were compared, in Reference Example B_2 (Fig. 8), the difference in polymer composition ratio and target composition of the polymer formed at the initial stage of the main step was large. In addition, about the polymer formed from the reaction time of 4 hours from the end of the main step (the end of the dropping liquid) to the reaction time of 7 hours as the end of the holding step, the polymer composition ratio and the target composition The difference becomes larger as time passes. ~ In contrast, in the main step, the example B-2 (Fig. 9) uses the composition of the above-mentioned factors to design the composition of the Sa, and the Tb of the target composition, and sets the supply after the end of the main step (the end of the dropwise addition of Tb). A total of 2 hours of the subsequent step of Uc, whereby in the main step, a polymer molecule having substantially the same composition as the target composition of 143 201222146 is generated from the beginning of the polymerization reaction, and the state continues at the end of the main step (reaction time 4 After the hour, the polymer composition ratio also showed a value very close to the target composition, and the deviation of the composition ratio caused by the reaction time was improved. [Refinement of Polymer] A mixed solvent of methanol and water (sterol/water = 80/20 capacity ratio) used in the purification step of the polymer of Example B-1, and (sterol/water == 90) /10 capacity ratio) was changed to a mixed solvent of methanol and water (methanol/water = 85/15 capacity ratio) and (sterol/water = 95/5 capacity ratio), in the same manner as in Example B-1. The polymer P2 was obtained from the polymerization solution in the flask which had passed the reaction time of 7 hours. The results of solubility evaluation of Mw and Mw/Mn of the polymer P2 are shown in Table 20. [Manufacture of resist composition] In the same manner as in Example B-1, a resist composition containing the polymer P2 was prepared, and the sensitivity was evaluated. The results are shown in Table 20. &lt;Reference Example B-3: Design of composition of solution Uc used in the subsequent step&gt; This example is obtained by the above formula (m-Ι), the following formula (m-6), and the following formula ( The monomer m-Ι, the monomer m-6, and the monomer m-7 represented by m-7) are polymerized, and the target composition is m-1 : m-6 : m-7 = 25 : 25 : 50 ( An example of the composition of Uc when the target of the weight average molecular weight is 10,000. As the polymerization initiator, the same dimethyl-2,2'-azobisisobutyrate as Reference Example B-1 was used, and the polymerization temperature was set to 8 (TC. 201222146 ^υ^οοριί

[化5][Chemical 5]

入口 衣虱軋環境下，將PGME 129.丨份加入至具備氮氣導 ，授拌機、冷凝器、滴液漏斗、及溫度計的燒瓶中。 放人至水浴中’―邊對燒瓶⑽行麟—邊將水浴 的&amp;度提高至8〇。〇。In the inlet and undercoating environment, PGME 129. 丨 was added to a flask equipped with a nitrogen gas guide, a mixer, a condenser, a dropping funnel, and a thermometer. Put the person into the water bath and move the flask to the flask (10) to increase the water bath to 8 〇. Hey.

觀内滴液料歷時4小時簡定的滴加速度向燒 滴加溶液，_將痛絲合起始劑的 單體叫Μ·95份（25莫耳^皿為止而使反應停止。 ，-6 26.87 份(25莫耳。/:): :體心7 39.65份（5〇莫耳 PGME 92.5 份、 9·130^ 自上述滴加溶液的滴加開始算起Q 5小時、！小時、2 145 201222146 小時、3小時、4小時、5小時、6 採樣燒瓶内的聚合反應溶液〇5 、、時、7小時後，分別 單體m-6、單體m-7的定量。夢此、刀別進行單體m-1、 瓶内的各單體的質量。其結果，可知各採樣時殘存於燒 時後與4小時後的結果如表12所=°。自滴加開始算起3小 [表12] 不。 ___丄（Mx) 單— 4.03 單體 ηΐ^~7ϊν1ζ) 繼而，使用各單體 燒瓶内的各單體的莫耳分率（相^成各採樣時殘存於 其結果’例如自滴加開始算起3二後Mz) : 結果如表13所示。 、灸，、4小時後的 [表 13]In the view, the drip material was added to the drip drop solution for a period of 4 hours, and the monomer of the pain-initiating initiator was Μ·95 parts (25 mol) and the reaction was stopped. 26.87 servings (25 mol./:): : Body volume 7 39.65 parts (5 〇 耳 PGME 92.5 parts, 9.130^ From the start of the above dropping solution, Q 5 hours, ! hours, 2 145 201222146 hours, 3 hours, 4 hours, 5 hours, 6 samples of the polymerization reaction solution in the flask 〇5, hour, 7 hours, respectively, the quantification of monomer m-6, monomer m-7. Dream this, knife The mass of each monomer in the monomer m-1 and the bottle was measured. As a result, it was found that the results after remaining at the time of each sampling and after 4 hours were as shown in Table 12. = ° from the start of the dropwise addition [ Table 12] No. ___丄(Mx) Single - 4.03 Monomer ηΐ^~7ϊν1ζ) Then, the molar fraction of each monomer in each monomer flask was used (the result is the same as the result of each sampling) For example, since the start of the drip addition, Mz): The results are shown in Table 13. Moxibustion, after 4 hours [Table 13]

_小時後（莫耳％) 18.71 26.16 55.13 以與參考例B-1相同的方式，求出各 成的聚合物中的單體單元的含有比率（聚人物％二所生 結果示於圖10。 （、口物組成）。將其 如圖10的結果所示，聚合物組成比 最=乍為目標組成的25 : 25 : 50者是自滴加開二P:) 小時後〜4小時後所生成的聚合物，為 方起3 ^-^2=24.32: 146 201222146 H-UZO〇plf 23.54 : 46.86。 若使用該值與自滴加開始算起的經過時間為3小時後 的 Mx : My : Mz 的值（表 13)，根據 Fx = Px/Mx、Fy = Py/My、Fz = Pz/Mz而求出因婁丈Fx、因數Fy、因數Fz，則 變成 Fx= 1.30、Fy=0.90、Fz=0.85。此時，根據 Fz&lt;Fy &lt;Fx，將Fz替換為0。 使用該因數的值與目標組成求出Uc的組成x〇 : y〇 :After _hour (mole %) 18.71 26.16 55.13 The content ratio of the monomer unit in each of the obtained polymers was determined in the same manner as in Reference Example B-1 (the results of the poly capita % are shown in Fig. 10). (, composition of the mouth). As shown in the results of Figure 10, the polymer composition ratio = 乍 is the target composition of 25: 25: 50 is from the addition of two P:) hours after ~ 4 hours The resulting polymer was from 3^-^2=24.32: 146 201222146 H-UZO〇plf 23.54: 46.86. If this value is used, the value of Mx : My : Mz after 3 hours elapsed from the start of the titration (Table 13), according to Fx = Px/Mx, Fy = Py/My, Fz = Pz/Mz When the factor Fx, the factor Fy, and the factor Fz are obtained, Fx = 1.30, Fy = 0.90, and Fz = 0.85 are obtained. At this time, Fz is replaced with 0 according to Fz&lt;Fy &lt;Fx. Use the value of this factor and the target composition to find the composition of Uc x〇 : y〇 :

z〇。 x〇 = 25xFx/ ( 25&gt;&lt;Fx +25&gt;&lt;Fy + 5〇xFz) = 25χ1·30/( 25x1.30 + 25x0.90 +5〇χ〇 ) = 59.1 莫耳％。 y〇 = 25xFy/ (25&gt;&lt;Fx + 25xFy + 5〇xFz) = 25x〇_90/(25x1.30 + 25x0.90 + 50x0)=40.9 莫耳％。 z〇=5〇xFz/ ( 25&gt;&lt;Fx+25&gt;&lt;Fy + 5〇xFz) = 5〇χ〇/ (25χ1.30 + 25χ〇_90 + 5〇χ〇) =0 莫耳 ％。 &lt;實例B-3&gt; 本例中，於事先將溶液Sa供給至反應器内，然後滴加 Tb及聚合起始劑溶液的主步驟後，設置滴加Uc的後步驟。 使用參考例B-3中所求出的Uc的組成。所使用的單 體的種類、聚合起始劑的種類、聚合溫度、聚合物的目標 組成、及重量平均分子量的目標值與參考例B-3相同。將 147 201222146 —Γ V/LW 上/X lZ〇. X〇 = 25xFx/ (25&gt;&lt;Fx +25&gt;&lt;Fy + 5〇xFz) = 25χ1·30/( 25x1.30 + 25x0.90 +5〇χ〇 ) = 59.1 % of the mole. Y〇 = 25xFy/ (25&gt;&lt;Fx + 25xFy + 5〇xFz) = 25x〇_90/(25x1.30 + 25x0.90 + 50x0)=40.9% by mole. Z〇=5〇xFz/ ( 25&gt;&lt;Fx+25&gt;&lt;Fy + 5〇xFz) = 5〇χ〇/ (25χ1.30 + 25χ〇_90 + 5〇χ〇) =0 Mo % . &lt;Example B-3&gt; In the present example, after the solution Sa was supplied to the reactor in advance, and then the main step of dropwise adding Tb and the polymerization initiator solution, a subsequent step of dropping Uc was set. The composition of Uc obtained in Reference Example B-3 was used. The target type of the monomer to be used, the type of the polymerization initiator, the polymerization temperature, the target composition of the polymer, and the target value of the weight average molecular weight were the same as those in Reference Example B-3. Will be 147 201222146 —Γ V/LW on /X l

Sa的單體組成設為與以使用上述因數的方法所設計的第i 組成相同，將Tb的單體組成設為與目標組成相同。 [Sa的第1組成的設計] 使用參考例B-3中所求出的因數的值（Fx=1 3〇、卜 = 0.90、Fz=0_85)與目標組成求出第i組成，將其作為 Sa的單體組成。 x〇〇 = 25/Fx = 25/1.30= 19.2 莫耳％。 y〇〇=25/Fy = 25/0.90 = 27.8 莫耳％。 z〇〇=50/Fz= 50/0.85 = 58.8 莫耳〇/0。 於氮氣環境下，將下述的Sa (S1)加入至具備氮氣導 入口、攪拌機、冷凝器、2個滴液漏斗、及溫度計的燒瓶 中。將燒瓶放入至水浴中，一邊對燒瓶内進行攪拌一邊將 水浴的溫度提高至80°C。 其後，自另一個滴液漏斗同時開始下述的Tb(Tl)與 聚合起始劑的供給，歷時4小時將Tb滴加至燒瓶内，歷 時2〇分鐘將聚合起始劑滴加至燒航内。進而，自剛結束 Tb的供給之後，歷時1小時滴加下述Uc中的8〇質量％ (U1)，然後歷時1小時滴加剩餘的2〇質量％ (U2)，進 而將8〇C的溫度保持1小時。自溶液几的滴加開始算起 7小時後’冷卻至室溫為止而使反應停止。 於本例中，Uc所含有的單體的合計量為總單體供給量 的1.99質量°/〇。 148 201222146 ^tu^oopif (Sa) 單體m-1 2.00份（18.2莫耳％)、 單體m-6 2.99份（26.2莫耳％)、 單體 m-7 4.74 份（55.6 莫耳0/〇)、 PGME 139.0 份。 (Tb) 單體m-1 23·36份（25莫耳％)、 • 單體m-6 24.19份（25莫耳％)、 單體m-7 39.57份（50莫耳％)、 PGME 44.5 份、 二曱基-2,2’-偶氮雙異丁酸酯2.815份（相對於Sa及 Tb中的單體的合計量為2.0莫耳％)。 (聚合起始劑溶液） PGME5.2 份、 二曱基-2,2’-偶氮雙異丁酸酯4.223份（相對於Sa及 Tb中的單體的合計量為3.0莫耳％)。 • (Uc) 單體m-1 1.25份（59.1莫耳％)、 單體m-6 0.73份（40.9莫耳％ )、 PGME 37.5 份、 二曱基-2,2'-偶氮雙異丁酸酯0.132份（相對於Uc中 的單體的合計量為5.0莫耳％)。 以與參考例B-1相同的程序，求出各反應時間内所生 成的聚合物中的單體單元的含有比率（聚合物組成比）。將 149 201222146, 其結果示於圖11。 若對圖10與圖11的結果進行比較，則參考例B 3(圖 10)中’於主步驟的初期所生成的聚合物的聚合物組成比 與目標組成的差較大。另外，關於自作為主步驟的結束（滴 加液的結束）時的反應時間4小時至作為保持步驟的結束 時的反應時間7小時之間所生成的聚合物，聚合物組^比 與目標組成的差隨時間經過而變大。 相對於此，實例B-3 (圖U)於主步驟中使用利用上 述因數設計單體組成的Sa、及目標組成的Tb，且於主步 _ 驟的結束（Tb的滴加結束）後設置供給合計2小時的uc 的後步驟，藉此於主步驟中，自剛開始聚合反應之後生成 與目標組成大致相同組成的聚合物分子，且該狀態持續， 於主步驟的結束（反應時間4小時）後，聚合物組成比亦 顯示與目標組成非常接近的值，由反應時間所引起的組成 比的偏差得到改善。 [聚合物的精製] 除將實例B-1的聚合物的精製步驟中所使用的曱醇及 鲁 水的混合溶劑（甲醇/水= 80/20容量比）、及（曱醇/水= 卯八0容量比）均變更為二異丙醚以外，以與實例B-1相 同的方式’自經過了 7小時的反應時間的燒瓶内的聚合反 應溶液獲得聚合物。將聚合物P3的Mw、Mw/Mn，溶 解性評價的結果示於表21。 &lt;參考例B - 4 :後步驟中所使用的溶液Uc的組成的設 計&gt; 150 201222146 HU^OOpif 本例是求出使由下述式（m_8)、下述式（m_9)、下述 10)所表示的單體m_8、單體m_9、單體m_i0進行 Γ 製造目標組成為 m_8 : m-9 : m-10 = 30 : 50 : 20 、耳/。）、重量平均分子量的目標值為】〇的聚合物 時的Uc的組成的例。 聚合起始劑使用與參考例相同的二曱基_2,2，_偶氮 雙異丁酸酯’聚合溫度設為8〇ΐ。 [化6] W 0~Λ 彳。The monomer composition of Sa is set to be the same as the ith composition designed by the method using the above factors, and the monomer composition of Tb is set to be the same as the target composition. [Design of the first composition of Sa] The ith component is obtained by using the value of the factor (Fx=1 3〇, Bu = 0.90, Fz=0_85) obtained in Reference Example B-3 and the target composition. The monomer composition of Sa. X〇〇 = 25/Fx = 25/1.30= 19.2 Moher%. Y〇〇=25/Fy = 25/0.90 = 27.8 Moher%. Z〇〇=50/Fz= 50/0.85 = 58.8 Moer/0. The following Sa (S1) was placed in a flask equipped with a nitrogen gas inlet, a stirrer, a condenser, two dropping funnels, and a thermometer under a nitrogen atmosphere. The flask was placed in a water bath, and the temperature of the water bath was raised to 80 ° C while stirring the inside of the flask. Thereafter, the following Tb (Tl) and the polymerization initiator were simultaneously supplied from another dropping funnel, and Tb was dropwise added to the flask over 4 hours, and the polymerization initiator was added dropwise to the mixture for 2 minutes. In the air. Further, immediately after the supply of Tb was completed, 8 〇 mass% (U1) in the following Uc was added dropwise over 1 hour, and then the remaining 2 〇 mass% (U2) was added dropwise over 1 hour, and further 8 〇C was added. The temperature was maintained for 1 hour. The reaction was stopped 7 hours after the start of the dropwise addition of the solution, and was cooled to room temperature. In the present example, the total amount of the monomers contained in Uc is 1.99 mass% / Torr of the total monomer supply amount. 148 201222146 ^tu^oopif (Sa) Monomer m-1 2.00 parts (18.2 mol%), monomer m-6 2.99 parts (26.2 mol%), monomer m-7 4.74 parts (55.6 Mo 0/ 〇), PGME 139.0 copies. (Tb) Monomer m-1 23·36 parts (25 mol%), • Monomer m-6 24.19 parts (25 mol%), monomer m-7 39.57 parts (50 mol%), PGME 44.5 Part, 2.815 parts of dimercapto-2,2'-azobisisobutyrate (2.0 mol% relative to the monomer in Sa and Tb). (Polymerization initiator solution) 5.2 parts of PGME and 4.223 parts of dimercapto-2,2'-azobisisobutyrate (3.0 mol% based on the total amount of monomers in Sa and Tb). • (Uc) monomer m-1 1.25 parts (59.1 mol%), monomer m-6 0.73 parts (40.9 mol%), PGME 37.5 parts, dimercapto-2,2'-azobisisobutyl The acid ester was 0.132 parts (5.0 mol% relative to the total amount of monomers in Uc). The content ratio (polymer composition ratio) of the monomer units in the polymer produced in each reaction time was determined by the same procedure as in Reference Example B-1. Will be 149 201222146, the results of which are shown in Figure 11. When the results of Fig. 10 and Fig. 11 are compared, the difference between the polymer composition ratio of the polymer produced in the initial stage of the main step and the target composition in Reference Example B 3 (Fig. 10) is large. In addition, regarding the polymer formed from the reaction time of 4 hours from the end of the main step (the end of the dropping liquid) to the reaction time of 7 hours as the end of the holding step, the polymer composition ratio and the target composition The difference becomes larger as time passes. On the other hand, in the main step, the example B-3 (Fig. U) uses the composition of the above-mentioned factors to design the composition of the sa, and the Tb of the target composition, and is set after the end of the main step (the end of the dropwise addition of Tb). The latter step of supplying uc for a total of 2 hours, whereby in the main step, a polymer molecule having a composition substantially the same as the target composition is generated from the beginning of the polymerization reaction, and the state continues, at the end of the main step (reaction time 4 hours) After that, the polymer composition ratio also showed a value very close to the target composition, and the deviation of the composition ratio caused by the reaction time was improved. [Refinement of polymer] A mixed solvent of decyl alcohol and lube water (methanol/water = 80/20 capacity ratio) used in the purification step of the polymer of Example B-1, and (sterol/water = 卯) The polymer was obtained from the polymerization solution in the flask which had passed the reaction time of 7 hours in the same manner as in Example B-1 except that the octagonal capacity ratio was changed to diisopropyl ether. The results of evaluation of solubility of Mw and Mw/Mn of the polymer P3 are shown in Table 21. &lt;Reference Example B-4: Design of composition of solution Uc used in the subsequent step&gt; 150 201222146 HU^OOpif This example is obtained by the following formula (m_8), the following formula (m_9), and the following 10) The indicated monomer m_8, monomer m_9, and monomer m_i0 are produced. The target composition is m_8 : m-9 : m-10 = 30 : 50 : 20 , ear /. The target value of the weight average molecular weight is an example of the composition of Uc when the polymer of ruthenium is used. As the polymerization initiator, the same dimercapto-2,2,-azobisisobutyrate as the reference example was used, and the polymerization temperature was set to 8 Torr. [Chem. 6] W 0~Λ 彳.

HO (m〜8) (m~9) (m-10) 於氮氣環境下，將PGMEA 82.8份加入至具備氮氣導 入口、攪拌機、冷凝器、滴液漏斗、及溫度計的燒瓶中。 將燒瓶放入至水浴中’ 一邊對燒瓶内進行攪拌一邊將水浴 的溫度提高至80°C。 其後’自滴液漏斗歷時4小時以固定的滴加速度向燒 瓶内滴加含有下述的單體混合物、溶劑、及聚合起始劑的 滴加溶液，進而將8〇°C的溫度保持3小時。自滴加溶液的 滴加開始算起7小時後，冷卻至室溫為止而使反應停止。 單體m-8 30.〇4份（30莫耳％)、 單體m-9 52.〇8份（5〇莫耳％)、 151 201222146 1Λ^〇 opif 單體m-10 17.22份（2〇莫耳％) PGMEA 149.0 份、 一 τ签叫两虱叉共丁酸j旨 總供給量為5.0莫耳％)- 自上述滴加溶液的滴加開始算起〇5小時 小時、3小時、4小時、5小時、6小 ^夺、 採樣燒_的聚合反應溶液Μ分'^分〕 單體m-9、單體一較HO (m~8) (m~9) (m-10) 82.8 parts of PGMEA was placed in a flask equipped with a nitrogen gas inlet, a stirrer, a condenser, a dropping funnel, and a thermometer under a nitrogen atmosphere. The temperature of the water bath was raised to 80 ° C while stirring the inside of the flask while placing the flask in a water bath. Thereafter, a dropping solution containing the following monomer mixture, solvent, and polymerization initiator was added dropwise from the dropping funnel to the flask at a fixed dropping rate for 4 hours, and the temperature of 8 ° C was maintained at 3 hour. Seven hours after the start of the dropwise addition of the dropwise addition solution, the reaction was stopped by cooling to room temperature. Monomer m-8 30.〇4 parts (30 mol%), monomer m-9 52.〇8 parts (5〇mol%), 151 201222146 1Λ^〇opif monomer m-10 17.22 parts (2 〇莫耳%) PGMEA 149.0 parts, one τ sign two 虱 共 共 共 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 旨 - - - - 〇 〇 〇 〇 〇 〇 〇 4 hours, 5 hours, 6 small ^, the sampling reaction _ the polymerization reaction solution ' ' ^ points) monomer m-9, monomer one

瓶内的各單體的質量。其結果 =寺殘存於i 時後與4小時後的結果如表14 ^如。自滴加開始算起h [表 14]The mass of each monomer in the bottle. The result = the result of the temple remaining after i and after 4 hours is as shown in Table 14. Since the start of the drop, h [Table 14]

繼而，使用各單體的分子量，換算 燒瓶:π體的莫耳分率(姆 結果Gts；：：0。自滴加開轉起3小時後與4小時後, [表 15] 皁體 m-8 (Mx) 3小時後（莫耳％) 90 ΠΠ 〜小時後 單體 γπ-9ΤΚΪΫ1 單體 m-l〇 (Μζ) ~ 4638 24.61 __ 28.67 ~~ ……二 40^5~' 30.67 152 201222146 *TWZ.O opif 以與參考例B-l相同的方式，求出各反應時段内所生 成的聚合物中的單體單元的含有比率（聚合物組成）。將其 結果示於圖12。 如圖12的結果所示，聚合物組成比（Px : Py : Pz) 最接近作為目標組成的30 : 50 : 20者是自滴加開始算起3 小時後〜4小時後所生成的聚合物，為Px:Py:Pz = 29.22 : 50.23 : 20.55。 若使用該值與自滴加開始算起的經過時間為3小時後 的 Mx ·· My : Mz 的值（表 15)，根據 Fx = Px/Mx、Fy = Py/My、Fz = Pz/Mz而求出因婁欠Fx、因數Fy、因數Fz，則 變成 Fx=1.01、Fy=1.08、Fz = 0.84。此時，根據 Fz&lt;Fx &lt;Fy，將Fz替換為0。 使用該因數的值與目標組成求出Uc的組成x〇 : y〇 : z〇 0 x〇 = 3〇xFx/ ( 3〇xFx+5〇xFy +2〇xFz) =3〇x 1.01/(3〇xl_01 +50x1.08 + 20x0) = 35.9 莫耳％。 y〇=5〇xFy/ (25&gt;&lt;Fx + 25xFy+5〇xFz) =50x1.08/(30x1.01+ 50x1.08 + 20x0 ) = 64.1 莫耳％。 z〇=2〇xFz/ (25&gt;&lt;Fx + 25xFy+5〇xFz) = 2〇χ〇/ (30x1.01 + 50x1.08 + 20x0) =0 莫耳％。 153 201222146 &lt;實例B-4&gt; 本例中，於事先將含有Sa組成的單體的一部分的溶液 =給，反應器内，然後滴加Tb&amp;Sa組成的單體的剩餘部 分與聚合起始劑溶液的主步驟後，設置滴加Uc的後步驟。 使用參考例B-4中所求出的Uc的組成。所使用的單 體的種類、聚合起始劑的種類、聚合溫度、聚合物的目標 組成、及重量平均分子量的目標值與參考例B-4相同。將 Sa的單體組成設為與以使用上述因數的方法所設計的第1 組成相同’將Tb的單體組成設為與目標組成相同。 [Sa的第1組成的設計] 使用參考例B_4中所求出的因數的值（Fx==1 〇1、 = 1.〇8、Fz = 〇.84)與目標組成求出第！組成，將其作 Sa的單體組成。 … x〇o = 30/Fx = 30/1.01 = 29.7 莫耳％。 y〇o==50/Fy=50/1.08 = 46.3 莫耳％。 z〇〇 = 20/Fz = 20/0.84 = 23.8 莫耳％。 於氮氣環境下’將下述的Sa的一部分（S1)加入至 具備氮氣導入口、攪拌機、冷凝器、2個滴液漏斗、及溫 度計的燒瓶中。將燒瓶放入至水浴中，一邊對燒瓶内進行 擾拌一邊將水浴的溫度提高至80¾。 其後’自另一個滴液漏斗同時開始下述的Tb ( T1 )、 及含有Sa的剩餘部分（S2)與聚合起始劑的溶液的供給， 154 201222146 ^rv/Aoopif 歷時4小時將Tb滴加至燒瓶内，歷時20分鐘將Sa的剩 餘部分及聚合起始劑滴加至燒瓶内。進而，自剛結束Tb 的供給之後，歷時1小時滴加下述Uc中的80質量％(111)， 然後歷時1小時滴加剩餘的20質量％ (U2)，進而將80°C 的溫度保持1小時。自溶液Tb的滴加開始算起7小時後， 冷卻至室溫為止而使反應停止。 於本例中，Uc所含有的單體的合計量為總單體供給量 Λ 的1.7質量％。 (含有Sa組成的單體的一部分的溶液） 單體m-8 2.97份（29.7莫耳％)、 單體m-9 4.82份（46.3莫耳％)、 PGMEA 101.5 份。 (Tb) 單體m-8 27.03份（30莫耳％)、 單體m-9 46.87份（50莫耳％)、 單體m-10 15.50份（20莫耳％)、 # PGMEA99.3 份、 二曱基-2,2’-偶氮雙異丁酸酯4.599份（相對於Sa及 Tb中的單體的合計量為2.0莫耳％)。 (Sa組成的單體的剩餘部分與聚合起始劑溶液） PGMEA 10.7 份、 單體 m-10 2.05 份（23.8 莫耳％)、 二曱基-2,2’-偶氮雙異丁酸酯4.599份（相對於Sa及 Tb中的單體的合計量為2.0莫耳％)。 155 201222146 (Uc) 單體m-8 0.61份（35 9莫耳％)、 年體m-9 1.12份（64.1莫耳％ )、 PGMEA 24.0 份、 ~ 二甲基_2,2'-偶氮雙異丁酸酉旨0.144份（相對於Uc中 的單體的合計量為4.0莫耳％)。 了眾uc〒 以與參考例B·1相同的程序，求出各反應時間内所生 單元的含有比率(聚合物-成比)。將Then, using the molecular weight of each monomer, the molar fraction of the flask: π body was converted (m result Gts;:: 0. After 3 hours from the dropwise addition and after 4 hours, [Table 15] soap body m- 8 (Mx) After 3 hours (% by mole) 90 ΠΠ ~ After the monomer γπ-9ΤΚΪΫ1 monomer ml〇(Μζ) ~ 4638 24.61 __ 28.67 ~~ ......二40^5~' 30.67 152 201222146 *TWZ. O opif The content ratio (polymer composition) of the monomer unit in the polymer produced in each reaction period was determined in the same manner as in Reference Example B. The results are shown in Fig. 12. It is shown that the polymer composition ratio (Px: Py: Pz) is the closest to the target composition of 30:50:20 is the polymer formed after 3 hours from the start of the dropwise addition to 4 hours, which is Px:Py: Pz = 29.22 : 50.23 : 20.55. If this value is used and the value of Mx ·· My : Mz after 3 hours from the start of the addition (Table 15), according to Fx = Px/Mx, Fy = Py /My, Fz = Pz/Mz, and find Fx, factor Fy, factor Fz, then Fx=1.01, Fy=1.08, Fz = 0.84. At this time, Fz is replaced according to Fz&lt;Fx &lt;Fy 0. Use the value of this factor and the target composition to find the composition of Uc x〇: y〇: z〇0 x〇= 3〇xFx/ ( 3〇xFx+5〇xFy +2〇xFz) =3〇x 1.01/ (3〇xl_01 +50x1.08 + 20x0) = 35.9 Moher%. y〇=5〇xFy/ (25&gt;&lt;Fx + 25xFy+5〇xFz) =50x1.08/(30x1.01+ 50x1.08 + 20x0 ) = 64.1 Mohr %. z〇=2〇xFz/ (25&gt;&lt;Fx + 25xFy+5〇xFz) = 2〇χ〇/ (30x1.01 + 50x1.08 + 20x0) =0 Mo Er 153 201222146 &lt;Example B-4&gt; In this example, a solution containing a part of a monomer having a Sa composition is given in advance, and the remainder of the monomer composed of Tb &amp; Sa is added dropwise to the polymerization reactor. After the main step of the initiator solution, a step of dropping Uc was provided. The composition of Uc determined in Reference Example B-4 was used. The type of monomer used, the type of polymerization initiator, the polymerization temperature, The target composition of the polymer and the target value of the weight average molecular weight were the same as in Reference Example B-4. The monomer composition of Sa was set to be the same as the first composition designed by the method using the above factors. The monomer composition of Tb was set to be the same as the target composition. [Design of the first composition of Sa] The value of the factor (Fx==1 〇1, = 1.〇8, Fz = 〇.84) obtained in Reference Example B_4 is used to determine the target composition! Composition, which is made up of the monomer composition of Sa. ... x〇o = 30/Fx = 30/1.01 = 29.7 % of the mole. Y〇o==50/Fy=50/1.08 = 46.3 Mo %. Z〇〇 = 20/Fz = 20/0.84 = 23.8 mole %. A part (S1) of the following Sa was added to a flask equipped with a nitrogen gas introduction port, a stirrer, a condenser, two dropping funnels, and a thermometer under a nitrogen atmosphere. The flask was placed in a water bath, and the temperature of the water bath was raised to 803⁄4 while disturbing the inside of the flask. Thereafter, the supply of the following Tb (T1) and the solution containing the remainder of the Sa (S2) and the polymerization initiator was started from another dropping funnel, 154 201222146 ^rv/Aoopif Tb drops for 4 hours It was added to the flask, and the remainder of Sa and the polymerization initiator were added dropwise to the flask over 20 minutes. Further, immediately after the supply of Tb was completed, 80% by mass (111) of the following Uc was added dropwise over one hour, and then the remaining 20% by mass (U2) was added dropwise over one hour, and the temperature at 80 ° C was further maintained. 1 hour. Seven hours after the start of the dropwise addition of the solution Tb, the reaction was stopped after cooling to room temperature. In the present example, the total amount of the monomers contained in Uc is 1.7 mass% of the total monomer supply amount Λ. (Solution containing a part of the monomer of Sa composition) 2.98 parts (29.7 mol%) of monomer m-8, 4.82 parts (46.3 mol%) of monomer m-9, and 101.5 parts of PGMEA. (Tb) monomer m-8 27.03 parts (30 mol%), monomer m-9 46.87 parts (50 mol%), monomer m-10 15.50 parts (20 mol%), # PGMEA 99.3 parts Further, 4.599 parts of dimercapto-2,2'-azobisisobutyrate (2.0 mol% relative to the monomers in Sa and Tb). (The remainder of the monomer composed of Sa and the polymerization initiator solution) PGMEA 10.7 parts, monomer m-10 2.05 parts (23.8 mole%), dimercapto-2,2'-azobisisobutyrate 4.599 parts (compared to 2.0 mol% of the monomers in Sa and Tb). 155 201222146 (Uc) Monomer m-8 0.61 parts (35 9 mol%), annual body m-9 1.12 parts (64.1 mol%), PGMEA 24.0 parts, ~ dimethyl 2,2'-azo The amount of diisobutyric acid was 0.144 parts (4.0 mol% relative to the total amount of monomers in Uc). In the same procedure as in Reference Example B.1, the content ratio (polymer-form ratio) of the unit produced in each reaction time was determined. will

12與圖13的結果進行比較，則參考例B-4(圖 12)中’於主步驟的初期所生成的聚合物的聚合物組成比 與目標組成的差較大。另外，關於自作為主步_結束（滴 加液的結束）時的反應時間4小時至作為保持步驟的結束 時的反應時間7小時之間所生成的聚合物，聚合物組成比 與目標組成的差隨時間經過而變大。When compared with the results of Fig. 13, the difference between the polymer composition ratio of the polymer produced in the initial stage of the main step and the target composition in Reference Example B-4 (Fig. 12) was large. In addition, about the polymer formed from the reaction time of 4 hours from the end of the main step_end (the end of the dropping solution) to the reaction time of 7 hours as the end of the holding step, the polymer composition ratio and the target composition The difference becomes larger as time passes.

相對於此，實例B-4 (圖13)於主步驟中使用利用上 述因數設計單體組成的Sa、及目標組成的Tb，且於主步 驟的結束（Tb的滴加結束）後設置供給合計2小時的Uc 的後步驟’藉此於主步驟中，自剛開始聚合反應之後生成 與目標組成大致相同組成的聚合物分子，且該狀態持續， 於主步驟的結束（反應時間4小時）後，聚合物組成比亦 顯示與目標組成非常接近的值，由反應時間所引起的組成 比的偏差得到改善。 [聚合物的精製] 156 201222146 HUZ5〇pif 除將實例B-l的聚合物的精製步驟中所使用的曱醇及 水的混合溶劑（甲醇/水= 80/20容量比）、及（甲醇/水= 90/10容量比）變更為甲醇及水的混合溶劑（曱醇/水=5〇/5〇 谷量比）、及（甲醇/水=60/40容罝比）以外，以與實例 B-1相同的方式’自經過了 7小時的反應時間的燒瓶内的 聚合反應溶液獲得聚合物P4。將聚合物P4的Mw、 Mw/Mn，溶解性評價的結果示於表21。 φ &lt;參考例B-5:後步驟中所使用的溶液Uc的組成的設 計&gt; 本例是求出使由上述式（m-l )、下述式（m_H )、下 述式（m·12)所表示的單體m-1、單體m-11、單體m-12 進行聚合，而製造目標組成為m-1 : m-11 : m-12 = 50 : 35 : 15 (莫耳％)、重量平均分子量的目標值為12,〇〇〇的聚合 物時的Uc的組成的例。 聚合起始劑使用與參考例B-1相同的二曱基-2,2，-偶氮 雙異丁酸酯，聚合溫度設為8(TC。 •[化 7]On the other hand, in the main step, the example B-4 (FIG. 13) uses the above-described factor to design the composition of the monomer Sa and the Tb of the target composition, and sets the total of the supply after the end of the main step (the end of the dropwise addition of Tb). The second step of Uc for 2 hours 'in this way, in the main step, a polymer molecule having a composition substantially the same as the target composition is generated from the beginning of the polymerization reaction, and the state continues, after the end of the main step (reaction time 4 hours) The polymer composition ratio also shows a value very close to the target composition, and the deviation of the composition ratio caused by the reaction time is improved. [Refining of polymer] 156 201222146 HUZ5〇pif A mixed solvent of methanol and water (methanol/water = 80/20 capacity ratio) used in the purification step of the polymer of Example B1, and (methanol/water = 90/10 capacity ratio) was changed to a mixed solvent of methanol and water (sterol/water = 5〇/5 grain ratio), and (methanol/water = 60/40 volume ratio), and Example B- 1 In the same manner 'Polymer P4 was obtained from the polymerization solution in the flask which had passed the reaction time of 7 hours. The results of solubility evaluation of Mw and Mw/Mn of the polymer P4 are shown in Table 21. φ &lt;Reference Example B-5: Design of composition of solution Uc used in the subsequent step&gt; This example is obtained by the above formula (ml), the following formula (m_H), and the following formula (m·12). The monomer m-1, monomer m-11, and monomer m-12 represented are polymerized, and the target composition is m-1 : m-11 : m-12 = 50 : 35 : 15 (mole %) An example in which the target value of the weight average molecular weight is 12 and the composition of Uc in the case of a polymer of ruthenium. As the polymerization initiator, the same dimercapto-2,2,-azobisisobutyrate as in Reference Example B-1 was used, and the polymerization temperature was set to 8 (TC.) [Chem. 7]

(m—11〉 (tn-1 2) 157 201222146 於氮氣環境下，將乳酸乙酯160.3份加入至具備氮氣 導入口、攪拌機、冷凝器、滴液漏斗、及溫度計的燒瓶中。 將燒瓶放入至水浴中，一邊對燒瓶内進行攪拌一邊將水浴 的溫度提高至80。〇 4 ,其後，自滴液漏斗歷時4小時以固定的滴加速度向燒 瓶内滴加含有下述的單舰合物、溶劑、及聚麵始劑ς 進而將80〇C的溫度保持3小時。自滴加溶液的 滴加，始，起7小時後，冷卻至室溫為止而使反應停止。 早體m-1 85.00份（5〇莫耳％)、 單體m-11 81.90份（35莫耳％)、 單體 m-12 25.50 份（15 莫耳°/〇)、 乳酸乙酯288.6份、 供給量雙異丁酸醋6.9〇份(相對於單體的總 自上述滴加溶液的滴加開始算起〇 小時、3小時、4小時、5小時、6小時^時、Η、時、2 採樣燒瓶内的聚合反應溶液〇5八小時後，分別 單體純、單體心的定量^^顺行單體心 燒瓶内的各單體的質量。其結果，例知各採樣時殘存於 小時後與4小時後的結果如=16所^_、。自滴加開始算起3 [表 16](m-11) (tn-1 2) 157 201222146 Under a nitrogen atmosphere, 160.3 parts of ethyl lactate was placed in a flask equipped with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, and a thermometer. In the water bath, the temperature of the water bath was raised to 80 while stirring the inside of the flask. 〇4, and then the single-hull compound containing the following was dropped from the dropping funnel over a period of 4 hours at a fixed dropping rate. Then, the solvent and the prepolymerization agent were further kept at a temperature of 80 ° C for 3 hours, and the reaction was stopped after 7 hours from the dropwise addition of the dropwise addition solution, and then cooled to room temperature. 85.00 parts (5 〇 mol%), monomer m-11 81.90 parts (35 mol%), monomer m-12 25.50 parts (15 mol/〇), ethyl lactate 288.6 parts, supply amount different 6.9 parts of butyric acid vinegar (the total amount of the monomer from the above-mentioned dropping solution is counted from the beginning of the hour, 3 hours, 4 hours, 5 hours, 6 hours, hour, hour, hour, 2 sampling flask After the polymerization reaction solution was 〇5 for eight hours, the monomers were pure and the monomer core was quantified. The monomers in the monomer flask were calibrated. By mass. As a result, when the known embodiment each sample remaining after hours and 4 hours after the results as _, ^ = 16 counting from the start of dropping 3 [Table 16]

卓體 m-l (Μχ) 單體 m-ll (Mv、 單體 m-12 (Mz) 灸（質量份) 26.34 1少時後（質量份） 16.47M-l (Μχ) monomer m-ll (Mv, monomer m-12 (Mz) moxibustion (mass) 26.34 1 after a small amount (mass) 16.47

158 201222146 πυζοοριί 繼而’使用各單體的分子量，換算成各採樣時殘存於 燒瓶内^各單體的莫耳分率（相當於MX:My:MZ)。 其釔果，例如自滴加開始算起3小時後與4小時後的 結果如表17所示。 [表 17] 單體 m-l (Mx) 單體 m-11 (My) 棋胁 m ΙΟN ^小旰後c冥耳％) 4小時後（莫耳％) — 48.17 46.26 42.01 49.82 早瓶 Π1-1Ζ (Mz) 9.82' 3.91 、以與參考例B-1柄同的方式，求出各反應時段内所生 成的聚合物巾料料元的含有比率（聚合物組成）。將其 結果示於圖14。 如圖14的結果所示，聚合物組成比（px : Py : PZ)158 201222146 πυζοοριί Then, the molecular weight of each monomer was converted into the molar fraction (corresponding to MX: My: MZ) of each monomer remaining in the flask at each sampling. The results, for example, after 3 hours from the start of the dropwise addition and after 4 hours, are shown in Table 17. [Table 17] Monomer ml (Mx) Monomer m-11 (My) Chess mmN ^小旰后c 耳%) 4 hours later (% by mole) — 48.17 46.26 42.01 49.82 Early bottle Π1-1Π ( Mz) 9.82' 3.91 The content ratio (polymer composition) of the polymer towel material produced in each reaction period was determined in the same manner as in the reference example B-1. The result is shown in Fig. 14. As shown in the results of Figure 14, the polymer composition ratio (px : Py : PZ)

”為目標組成的50 : 35 : 15者是自滴加開始算起3 小時後〜4小時後所生成的聚合物，為ρχ : p 49 99 · 34.55 ： 15.45 〇 若使用4值與自滴加開始算起的經過時間為3小時後 的Mx : My : Mz的值（表n)，根據Fx巧她、f户 Py/My、Fz = pz/Mz而求出因數Fx、因數Fy、因數Fz，則 變成 fx=1.04、Fy=0.82、Fz=157。此時根據 Fz&lt;Fx &lt;Fy，將Fy替換為〇。 使用該因數的值與目標組成求出Uc的組成x〇:y〇 z〇 0 159 201222146 x〇=5〇xFx/ (5〇xFx+35xFy+i5xF2) -5〇x1.〇4/(5〇x1.〇4 + 35x〇+ 15x1 57) = 68 8 ^4%〇 y〇=35xFy/ (5〇xFx + 35xFy+i5xF2) = 35X〇/(5〇XL〇4 + 35x〇+15x1.57) =0^^〇/o〇 z〇=15xFz/ (50xFx + 35xFy+i5xF2) = 15χ1·57/(5〇χ1.〇4 + 35χ〇+15χΐ57) = 31.2 莫耳％。The target composition of 50:35:15 is the polymer produced after 3 hours from the start of the dropwise addition, and is ρχ : p 49 99 · 34.55 : 15.45 〇 If using 4 values and self-drip The elapsed time from the beginning of 3 hours is the value of Mx : My : Mz (Table n), and the factor Fx, the factor Fy, the factor Fz are obtained according to Fx, P, Py/My, Fz = pz/Mz. Then, it becomes fx=1.04, Fy=0.82, Fz=157. At this time, Fy is replaced with 〇 according to Fz&lt;Fx &lt;Fy. The composition of Uc is obtained by using the value of the factor and the target composition x〇:y〇z 〇0 159 201222146 x〇=5〇xFx/ (5〇xFx+35xFy+i5xF2) -5〇x1.〇4/(5〇x1.〇4 + 35x〇+ 15x1 57) = 68 8 ^4%〇y 〇=35xFy/ (5〇xFx + 35xFy+i5xF2) = 35X〇/(5〇XL〇4 + 35x〇+15x1.57) =0^^〇/o〇z〇=15xFz/ (50xFx + 35xFy+i5xF2 ) = 15χ1·57/(5〇χ1.〇4 + 35χ〇+15χΐ57) = 31.2 mol%.

&lt;實例B-5&gt; 錢ΐ例切含有Sa㈣的單體的驗供給至万 一内，α後滴加Tb及聚合起始劑溶液的主步驟後，言; 置滴加Uc的後步驟。&lt;Example B-5&gt; A sample of a monomer containing Sa (tetra) was cut into a sample, and after the main step of adding Tb and a polymerization initiator solution after α, the subsequent step of dropping Uc was carried out.

使用參考例B-5中所求出的Uc的組成。所使用的單 體的種類、聚合起始劑的種類、聚合溫度、聚合物的目標 組成、及重量平均分子量的目標值與參考例B-5相同。將 Sa的單體組成設為與以使用上述因數的方法所設計的第1 組成相同’將Tb的單體組成設為與目標組成相同。 [Sa的第1組成的設計] 使用參考例B-5中所求出的因數的值（Fx=1.〇4、Fy = 0.82、Fz=l.57)與目標組成求出第1組成，將其作為 Sa的單體組成。 160 201222146 HUZOOpif x00 = 50/^ = 50/1.04 = 48.1 莫耳0/o。 y〇〇 = 35/Fy=35/0.82^42·7 0 200=15/^=15/1.57===9.6 莫耳〇/o。 於氮氣環境下，將下述的Sa (S1)加入至具備氮氣導 入口、攪拌機 '冷凝器、2個滴液漏斗、及溫度計的燒瓶The composition of Uc determined in Reference Example B-5 was used. The target type of the monomer to be used, the type of the polymerization initiator, the polymerization temperature, the target composition of the polymer, and the target value of the weight average molecular weight were the same as those in Reference Example B-5. The monomer composition of Sa was set to be the same as the first composition designed by the method using the above factors. The monomer composition of Tb was set to be the same as the target composition. [Design of the first composition of Sa] The first component is obtained by using the values of the factors (Fx=1.〇4, Fy=0.82, Fz=l.57) obtained in Reference Example B-5 and the target composition. It is made up as a monomer of Sa. 160 201222146 HUZOOpif x00 = 50/^ = 50/1.04 = 48.1 Moor 0/o. Y〇〇 = 35/Fy=35/0.82^42·7 0 200=15/^=15/1.57===9.6 Moer/o. The following Sa (S1) was added to a flask equipped with a nitrogen inlet, a condenser 'condenser, two dropping funnels, and a thermometer under a nitrogen atmosphere.

中。將燒瓶放入至水浴中，一邊對燒瓶内進行攪拌一邊將 水浴的溫度提高至80。〇。 其後，自另個滴液漏斗同時開始下述的Tb ( T1)與 聚合起始劑的供給’歷時4小時將Tb滴加至燒瓶内，歷 時20刀*將聚Q ^始劑滴加至燒瓶内。進而，自剛結束 時1小時滴加下述❿中的80質量％ 而將m:的溫度保持加剩餘的20質量％ (U2)，進 7小時後，冷卻至室溫為;;夺。自溶液Tb_加開始算起 ττ 為止而使反應停止。 的13;質^%。 ^所含有的單體的合計量為總單體供給量 (Sa) 、旲耳％)、 單體 m-11 9.99 份， w、42·7 箪耳〇/n). 單體 m-12 1.62 份斗） 乳酸乙酯196.5份。 (Tb) (5〇莫耳％)、 單體m-1 76.50份 161 201222146 ~Γ υριί 單體m-11 73.71份（35莫耳％)、 單體m-12 22.95份（15莫耳％)、 乳酸乙酯218.2份、 二曱基-2,2'-偶氮雙異丁酸酯2.531份（相對於Sa及 Tb中的單體的合計量為1.1莫耳％)。 (聚合起始劑溶液） 乳酸乙酯5.9份、 二甲基-2,2’-偶氮雙異丁酸酯2.531份（相對於Sa及 Tb中的單體的合計量為1.1莫耳％)。 (Uc) 單體m-1 1.77份（68.8莫耳％)、 單體m-12 0.8份（31.2莫耳％)、 乳酸乙酯24.0份、 二曱基-2,2'-偶氮雙異丁酸酯0.076份（相對於Uc中 的單體的合計量為2.2莫耳％)。 以與參考例B-1相同的程序，求出各反應時間内所生 成的聚合物中的單體單元的含有比率（聚合物組成比）。將 其結果示於圖15。 若對圖14與圖15的結果進行比較，則參考例B-5(圖 14)中，於主步驟的初期所生成的聚合物的聚合物組成比 與目標組成的差較大。另外，關於自作為主步驟的結束（滴 加液的結束）時的反應時間4小時至作為保持步驟的結束 時的反應時間7小時之間所生成的聚合物，聚合物組成比 與目標組成的差隨時間經過而變大。 162 201222146 H-UZ-OOpif 相對於此，實例B-5 (圖15)於主步驟中使用利用上 述因數設計單體組成的Sa、及目標組成的Tb，且於主步 驟的結束（Tb的滴加結束）後設置供給合計2小時的Uc 的後步驟，藉此於主步驟中，自剛開始聚合反應之後生成 與目標組成大致相同組成的聚合物分子，且該狀態持續， 於主步驟的結束（反應時間4小時）後，聚合物組成比亦 顯示與目標組成非常接近的值，由反應時間所引起的組成 比的偏差得到改善。 [聚合物的精製] 除將實例B-1的聚合物的精製步驟中所使用的曱醇及 水的混合溶劑（甲醇/水二80/20容量比）、及（甲醇/水= 90/10容量比）變更為曱醇及水的混合溶劑（曱醇/水= 70/30 容量比）、及（曱醇/水=80/2〇容量比）以外’以與實例 B-1相同的方式，自經過了 7小時的反應時間的燒瓶内的 聚合反應溶液獲得聚合物P5。將聚合物P5的Mw、 Mw/Mn，溶解性評價的結果示於表21。 &lt;參考例B-6 ··後步驟中所使用的溶液Uc的組成的設 計&gt; 本例是求出使由上述式上述式（m-11)、下 述式0-13)所表示的單體心丨、單體m ll、單體m l3 進行t合’而製造目標組成為m_l : m_U : m_i3 = 5〇 : 40 : 1〇 (莫耳％)、重量平均分子量的目標值為7 〇〇〇的聚合物 時的Uc的組成的例。 聚合起始劑使用與參考例B—i相同的二曱基_2,2，_偶氮 163 201222146 雙異丁酸酯’聚合溫度設為8(TC。 [化8] 0in. The flask was placed in a water bath, and the temperature of the water bath was raised to 80 while stirring the inside of the flask. Hey. Thereafter, Tb (T1) and the supply of the polymerization initiator were simultaneously started from another dropping funnel. Tb was added dropwise to the flask over 4 hours, and the poly-Q initiator was added dropwise to 20 knives*. Inside the flask. Further, 80% by mass of the following crucible was added dropwise from the end of the first hour, and the temperature of m: was kept to the remaining 20% by mass (U2), and after 7 hours, it was cooled to room temperature; The reaction was stopped from the beginning of the solution Tb_ plus ττ. 13; quality ^%. ^The total amount of monomers contained is the total monomer supply (Sa), 旲%), monomer m-11 9.99 parts, w, 42·7 箪 〇 / n). Monomer m-12 1.62斗)) Ethyl lactate 196.5 parts. (Tb) (5〇mol%), monomer m-1 76.50 parts 161 201222146 ~Γ υριί monomer m-11 73.71 parts (35 mole%), monomer m-12 22.95 parts (15 mole%) 218.2 parts of ethyl lactate and 2.531 parts of dimercapto-2,2'-azobisisobutyrate (1.1 mol% based on the total amount of monomers in Sa and Tb). (Polymerization initiator solution) 5.9 parts of ethyl lactate and 2.531 parts of dimethyl-2,2'-azobisisobutyrate (1.1 mol% based on the total amount of monomers in Sa and Tb) . (Uc) monomer m-1 1.77 parts (68.8 mol%), monomer m-12 0.8 parts (31.2 mol%), ethyl lactate 24.0 parts, dimercapto-2,2'-azo diiso Butyrate 0.076 parts (2.2 mol% relative to the total amount of monomers in Uc). The content ratio (polymer composition ratio) of the monomer units in the polymer produced in each reaction time was determined by the same procedure as in Reference Example B-1. The result is shown in Fig. 15. When the results of Fig. 14 and Fig. 15 were compared, in Reference Example B-5 (Fig. 14), the difference in the polymer composition ratio of the polymer formed at the initial stage of the main step and the target composition was large. In addition, about the polymer formed from the reaction time of 4 hours from the end of the main step (the end of the dropping liquid) to the reaction time of 7 hours as the end of the holding step, the polymer composition ratio and the target composition The difference becomes larger as time passes. 162 201222146 H-UZ-OOpif In contrast, Example B-5 (Fig. 15) uses the above-mentioned factors to design the Sa composition of the monomer and the Tb of the target composition in the main step, and at the end of the main step (the drop of Tb) After the addition), a subsequent step of supplying a total of 2 hours of Uc is set, whereby in the main step, a polymer molecule having a composition substantially the same as the target composition is generated from the beginning of the polymerization reaction, and the state continues, at the end of the main step. After the reaction time (4 hours), the polymer composition ratio also showed a value very close to the target composition, and the deviation of the composition ratio caused by the reaction time was improved. [Refinement of polymer] A mixed solvent of sterol and water (methanol/water ratio of 80/20) used in the purification step of the polymer of Example B-1, and (methanol/water = 90/10) The capacity ratio was changed to a mixed solvent of sterol and water (sterol/water = 70/30 capacity ratio), and (sterol/water = 80/2 〇 capacity ratio) 'in the same manner as in Example B-1 The polymer P5 was obtained from the polymerization solution in the flask which had passed the reaction time of 7 hours. The Mw and Mw/Mn of the polymer P5 and the results of solubility evaluation are shown in Table 21. &lt;Reference Example B-6 · Design of composition of solution Uc used in the subsequent step&gt; This example is obtained by expressing the above formula (m-11) and the following formula: 0-13) The monomer core, the monomer m ll, and the monomer m l3 are t-' and the target composition is m_l : m_U : m_i3 = 5〇: 40 : 1〇 (mole %), and the target value of the weight average molecular weight is 7 An example of the composition of Uc when a polymer is ruthenium. As the polymerization initiator, the same dimercapto-2,2,_azo 163 201222146 diisobutyrate was used as in Reference Example B-i. The polymerization temperature was set to 8 (TC.) [Chem. 8]

份加入見下將PGMEA130.2份與γ-丁内醋( 及溫产^植氮氣導入口、授摔機、冷凝器、滴液漏2 進;；。將燒瓶放入至水浴中’-邊對創 ,邊將水洛的溫度提高至80。(：。For the addition, add 130.2 parts of PGMEA and γ-butane vinegar (and the temperature of the nitrogen inlet, the drop machine, the condenser, and the drip leakage;; put the flask into the water bath'-side For the creation, increase the temperature of the water to 80. (:.

瓶内含時义小時以固定的滴加物 滴加溶液，，、溶劑、及聚合起始湾 滴加門残# 7 度保持3小時。自滴加溶深 ϋιη 1 85Γ夺後’冷卻至室溫為止而使反應停』 早體m-1 85.00份（5〇莫耳％)、 單體m-11 93.60份（4〇莫耳％)、 單體m-13 49.60份（1〇莫耳％)、 PGMEA 242.3 份、 γ-丁内酯100.0份、 164 201222146 W/δδρΐί _俯虱雙異丁酸酿4 八, 供給置為2.0莫耳％ )。 刀（相對於單體的總 自上述滴加溶液的滴加開始算起〇 小時、3小時、4小時、5小時、6 μ時、1小時、2 採樣燒瓶内的聚合反應溶液 八' 7小時後，分別 事韙m-η、單體m_】3的定量。:刀别進行單體m·!、 燒瓶内的各單體的質量。其結采樣時殘存於 小時後與4小時後的結果如表18所^。自滴加開始算起3 [表 18]The bottle contains the hourly drop of the solution with a fixed drop, the solvent, and the polymerization start bay. The residue is kept at 7 degrees for 3 hours. After the dropwise addition of deep ϋιη 1 85, the reaction was stopped after cooling to room temperature. Early body m-1 85.00 parts (5 〇 mol%), monomer m-11 93.60 parts (4 〇 mol%) , monomer m-13 49.60 parts (1〇 mol%), PGMEA 242.3 parts, γ-butyrolactone 100.0 parts, 164 201222146 W/δδρΐί _ 虱 虱 bis isobutyric acid brewed 4 八, supply set to 2.0 m %). The scalpel (relative to the total amount of the monomer from the dropwise addition of the above-mentioned dropping solution starts from hour, 3 hours, 4 hours, 5 hours, 6 μh, 1 hour, 2 samples of the polymerization solution in the sample flask for 8 '7 hours After that, the quantification of m-η and monomer m_]3 was carried out separately: the mass of each monomer in the flask was carried out in the monomer m·!, and the result of the residue remaining after the hour and 4 hours after the sampling As shown in Table 18 ^. Since the start of the addition of 3 [Table 18]

繼而，使用各單體的分子量，換算成 蟓瓶内的各單體的財分率（相#^Μχ : My ;則。子、Then, using the molecular weight of each monomer, it is converted into the profit ratio of each monomer in the bottle (phase #^Μχ: My;

其結果，例如自滴加開始算起3小時後與4 结果如表19所示。 、 [表 19] 3小時後（莫耳％) 一 47.39 '~ 44.62 4 小時 ~~ 45^05 - 49^69~~~~~As a result, for example, 3 hours after the start of the dropwise addition and 4 results are shown in Table 19. [Table 19] After 3 hours (% of Moer) A 47.39 '~ 44.62 4 hours ~~ 45^05 - 49^69~~~~~

單體 m-l (Μχ) ~Ml (My) 「13 (Mz) 以與參考例B-1相同的方式，求出各反應時段内所生 成的聚合物中的單體單元的含有比率（聚合物組成將其 165 201222146 結果示於圖16。 如圖16的結果所示，聚合物組成比（Px : Py : Pz) 最接近作為目標組成的50:40: 10者是自滴加開始算起3 小時後〜4小時後所生成的聚合物，為Px : Py: Pz = 49.85 : 39.28 : 10.87。 若使用該值與自滴加開始算起的經過時間為3小時後 的 Mx : My : Mz 的值（表 19)，根據 Fx = Px/Mx、Fy = Py/My、Fz = Pz/Mz而求出因數Fx、因數Fy、因數Fz，則 變成 Fx= 1·05、Fy=0.88、Fz= 1.36。此時，根據 Fz&lt;Fx &lt;Fy，將Fy替換為0。 使用該因數的值與目標組成求出Uc的組成x〇 : y〇 :Monomer ml (Μχ) ~Ml (My) "13 (Mz) The content ratio of the monomer unit in the polymer formed in each reaction period was determined in the same manner as in Reference Example B-1 (polymer composition) The result of 165 201222146 is shown in Fig. 16. As shown in the results of Fig. 16, the polymer composition ratio (Px: Py: Pz) is closest to the target composition of 50:40: 10 is 3 hours from the start of the dropwise addition. The polymer formed after ~4 hours is Px : Py: Pz = 49.85 : 39.28 : 10.87. If this value is used, the value of Mx : My : Mz after 3 hours elapsed from the start of the addition (Table 19), the factor Fx, the factor Fy, and the factor Fz are obtained according to Fx = Px/Mx, Fy = Py/My, Fz = Pz/Mz, and then Fx = 1·05, Fy = 0.88, Fz = 1.36. At this time, according to Fz&lt;Fx &lt;Fy, Fy is replaced with 0. The value of the factor and the target composition are used to find the composition of Uc x〇: y〇 :

Zo。 x〇=5〇xFx/ ( 5〇xFx + 4〇xFy+l〇xFz) = 5〇xl .05/( 50x1.05 + 40x0+ 1〇χ1.36 ) = 79.4 莫耳 ％。 y0 = 4〇xFy/ (5〇xFx + 4〇xFy+l〇xFz) = 4〇χ〇/ (50x1.05 + 40x0+ 1〇χ1·36) =0 莫耳0/〇。 z〇=l〇xFz/ ( 5〇xFx + 4〇xFy + l〇xFz) =l〇xl.36/( 50x1.05 + 40x0+ 10x1.36)= 20.6 莫耳0/〇。 &lt;實例B-6&gt; 本例中，於事先將含有Sa組成的單體的溶液供給至反 166 201222146 4UZ8«pif 應器内’ S後滴加Tb及聚合起始·液的主步驟後，設 置滴加Uc的後步驟。 使用參考例B_6中所求出的Uc的組成。所使用的單 體的種類、聚合起始劑的種類、聚合溫度、聚合物的目標 組成、及重量平均分子量的目標值與參考例B_6相同。將 Sa的單體組成設為與以使用上述因數的方法所設計的第i 組成相同，將Tb的單體組成設為與目標組成相同。 [Sa的第1組成的設計] 使用參考例B-6中所求出的因數的值（fx=i.〇5、Fy = 〇·88、FZ=1.36)與目標組成求出第1組成，將其作為 Sa的單體組成。 x〇o=50/Fx= 50/1.05 = 47.6 莫耳％。 y〇〇 = 40/Fy = 40/0.88 = 45.5 莫耳％。 z00=l〇/Fz= 10/1.36 = 7.4 莫耳％。 於氮氣環境下’將下述的Sa (S1 )加入至具備氮氣導 入口、攪拌機、冷凝器、2個滴液漏斗、及溫度計的燒瓶 中將燒瓶放入至水谷中，一邊對燒瓶内進行擾摔一邊將 水浴的溫度提高至80°C。 其後，自另一個滴液漏斗同時開始下述的Tb (T1)與 聚合起始劑的供給’歷時4小時將Tb滴加至燒瓶内，歷 時20分鐘將聚合起始劑滴加至燒瓶内。進而，自剛結束 Tb的供給之後，歷時1小時滴加下述Uc中的8〇質量％ 167 201222146 HUZOOpil (Ul)，然後歷時1小時滴加剩餘的20質量％ (U2)，進 而將80°C的溫度保持1小時。自溶液Tb的滴加開始算起 7小時後，冷卻至室溫為止而使反應停止。 於本例中，Uc所含有的單體的合計量為總單體供給量 的1.3質量％。 (Sa) 單體m-1 8.10份（47.6莫耳％)、 單體 m-11 10.64 份（45.5 莫耳％)、 單體 m-13 3.65 份（7.4 莫耳％)、 ® PGMEA 160.7 份、 γ-丁内酯70.0份。 (Tb) 單體m-1 76.50份（50莫耳％)、 單體m-11 84.24份（40莫耳％)、 單體m-13 44.64份（10莫耳％)、 PGMEA 187.7 份、 γ-丁内酯70.0份、 鲁 二甲基-2,2'-偶氮雙異丁酸酯1.726份（相對於Sa及 Tb中的單體的合計量為0.75莫耳％)。 (聚合起始劑溶液） PGMEA 6.9 份、 二曱基-2,2’-偶氮雙異丁酸酯1.726份（相對於Sa及 Tb中的單體的合計量為0.75莫耳％)。 (Uc) 168 201222146 WZOQpif 單體 m-1 1·79 份（79.4 莫耳。/〇)、 單體 m-13 1.35 份（20.6 莫耳％)、 PGMEA33.5 份、 γ-丁内酯10.0份、 份（相對於Uc中 一曱基-2,2'-偶氮雙異丁酸g旨0.076 的單體的合計量為2.2莫耳。/〇)。 以與參考例B-1相同的程序，求出各Zo. X〇=5〇xFx/ ( 5〇xFx + 4〇xFy+l〇xFz) = 5〇xl .05/( 50x1.05 + 40x0+ 1〇χ1.36 ) = 79.4 mol %. Y0 = 4〇xFy/ (5〇xFx + 4〇xFy+l〇xFz) = 4〇χ〇/ (50x1.05 + 40x0+ 1〇χ1·36) =0 Mo 0/〇. Z〇=l〇xFz/ ( 5〇xFx + 4〇xFy + l〇xFz) =l〇xl.36/( 50x1.05 + 40x0+ 10x1.36)= 20.6 Mo 0/〇. &lt;Example B-6&gt; In this example, a solution containing a monomer having a Sa composition is supplied to a main step of adding a Tb and a polymerization starting liquid after the 'S 2012 146 4UZ8 «pif reactor Set the post-step of dropping Uc. The composition of Uc found in Reference Example B_6 was used. The target type of the monomer to be used, the type of the polymerization initiator, the polymerization temperature, the target composition of the polymer, and the target value of the weight average molecular weight were the same as in Reference Example B-6. The monomer composition of Sa was set to be the same as the ith composition designed by the method using the above factors, and the monomer composition of Tb was set to be the same as the target composition. [Design of the first composition of Sa] The first component is obtained by using the value of the factor (fx=i.〇5, Fy = 〇·88, FZ=1.36) obtained in Reference Example B-6 and the target composition. It is made up as a monomer of Sa. X〇o=50/Fx= 50/1.05 = 47.6 Moher%. Y〇〇 = 40/Fy = 40/0.88 = 45.5 % of the mole. Z00=l〇/Fz= 10/1.36 = 7.4 mole %. The following Sa (S1) was added to a flask equipped with a nitrogen gas introduction port, a stirrer, a condenser, two dropping funnels, and a thermometer under a nitrogen atmosphere, and the flask was placed in a water valley while disturbing the inside of the flask. Wrestling raises the temperature of the water bath to 80 °C. Thereafter, the following Tb (T1) and the supply of the polymerization initiator were simultaneously started from another dropping funnel. Tb was added dropwise to the flask over 4 hours, and the polymerization initiator was added dropwise to the flask over 20 minutes. . Further, immediately after the supply of Tb was completed, 8 〇 mass% 167 201222146 HUZOOpil (Ul) in the following Uc was added dropwise over 1 hour, and then the remaining 20 mass% (U2) was added dropwise over 1 hour, and then 80° was further added. The temperature of C was maintained for 1 hour. Seven hours after the start of the dropwise addition of the solution Tb, the reaction was stopped by cooling to room temperature. In the present example, the total amount of the monomers contained in Uc is 1.3% by mass based on the total monomer supply amount. (Sa) monomer m-1 8.10 parts (47.6 mol%), monomer m-11 10.64 parts (45.5 mol%), monomer m-13 3.65 parts (7.4 mol%), ® PGMEA 160.7 parts, Γ-butyrolactone 70.0 parts. (Tb) monomer m-1 76.50 parts (50 mol%), monomer m-11 84.24 parts (40 mol%), monomer m-13 44.64 parts (10 mol%), PGMEA 187.7 parts, γ 70.0 parts of butyrolactone and 1.726 parts of lu-dimethyl-2,2'-azobisisobutyrate (0.75 mol% relative to the total amount of monomers in Sa and Tb). (Polymerization initiator solution) PGMEA 6.9 parts of dimercapto-2,2'-azobisisobutyrate 1.726 parts (0.75 mol% based on the total amount of monomers in Sa and Tb). (Uc) 168 201222146 WZOQpif monomer m-1 1·79 parts (79.4 mol./〇), monomer m-13 1.35 parts (20.6 mol%), PGMEA 33.5 parts, γ-butyrolactone 10.0 parts The total amount of the monomers (relative to the mono-alkyl-2,2'-azobisisobutyric acid g of 0.076 in Uc is 2.2 moles / 〇). Find the respective procedures in the same procedure as in Reference Example B-1.

成的聚合物㈣單體單元的含有_ (聚㈣姐 其結果示於圖17。 谓、、且成比）。將 與圖η的結果進行比較，則參考例μ(圖 16)中，於主.步驟的初期所生成的聚合物的聚合物组成比 與目標組成的差較大。另外，關於自作為主步驟的結束（滴 加液的結束）時的反應時間4小時至作為保持步驟的結束 時的反應時間7小時之間所生成㈣合物，聚合物組成比 與目標組成的差隨時間經過而變大。 相對於此，貫例B-6 (圖17)於主步驟中使用利用上 述因數設計單體組成的Sa、及目標組成的Tb，且於主步 驟的結束（Tb的滴加結束）後設置供給合計2小時的Uc 的後步驟，藉此於主步驟中，自剛開始聚合反應之後生成 與目標組成大致相同組成的聚合物分子，且該狀態持續， 於主步驟的結束（反應時間4小時）後，聚合物組成比亦 顯示與目標組成非常接近的值，由反應時間所引起的組成 比的偏差得到改善。 [聚合物的精製] 169 201222146 -τν/^,υυ^ιχ 除將實例Β-1的聚合物的精製步驟中所使用的曱醇及 水的混合溶劑（甲醇/水= 80/20容量比）、及（甲醇/水= 90/10容量比）變更為異丙醚以外，以與實例Β-1相同的 方式’自經過了 7小時的反應時間的燒瓶内的聚合反應溶 液獲得聚合物Ρ6。將聚合物Ρ6的Mw、Mw/Mn，溶解性 評價的結果示於表21。 &lt;比較例B-2〜比較例B-7 &gt; 於參考例〜參考例B-6中，使用經過了 7小時的 反應時間後，冷卻至室溫為止而使反應停止所獲得的燒瓶 内的聚合反應溶液，參考例Β·1以與實例的聚合物的 精製步驟相同的方式獲得比較聚合物，參考例Β-2以與實 例Β-2的聚合物的精製步驟相同的方式獲得比較聚合物， 參考例Β-3以與實例Β_3的聚合物的精製步驟相同的方式 獲得比較聚合物，參考例Β_4以與實例Β_4的聚合物的精 製步驟相同的方式獲得比較聚合物，參考例Β_5以與實例 Β-5的聚合物的精製步驟相同的方式獲得比較聚合物，參 考例Β-6以與貫例Β-6的聚合物的精製步驟相同的方式猝 得比較聚合物。針對所獲得的比較聚合物，以與實例 相同的方式求出Mw、Mw/Mn，並進行溶解性評價。將比 較例B-2、比較例B-3的結果示於表20，將比較二β_4^ 比較例B-7的結果示於表21。 另外，於比較例^B-2、比較例B-3中，使用所獲得的 比較聚合物’以與實例B-1相同的方式製備抗蝕&amp;組 物，並評價感光度。將其結果不於表20。 170 201222146 ^tUZQOpif [表 20] Mw Mw/Mn _______ 溶解性 [添加庚烷量（wt%)] Ϊ 感光度 (mJ/cm2 ) 實例B-1 10500 1.62 14.2___ 1.01 比較例B-1 10700 1.67 ' 10.8 1.72 比較例B-2 (參考例 B-1) 10600 1.75 ---- ...____ 11.6 1.65 實例B-2~~ 8400 1.58 6.15 0.51 比較例B-3 (參考例 B-2) 7400 1.65 5.7 0.78 根據表20的結果，實例B-l (主步驟+後步驟中滴加 的uc中所含有的單體合計量：215質量0/〇)中所獲得的聚 合物與比較例B-1 (後步驟中滴加的uc中所含有的單體合 計量：14.9質量％)、比較例B-2 (無主步驟、後步驟的區 別而全部以固定的比例滴加）中所獲得的聚合物相比，溶 解性顯著地提昇，且製成抗飯劑組成物時的感光度提昇。 另外，後步驟中滴加的溶液Uc所含有的單體的合計量未 被適當地控制的比較例B-1與實例B-1相比，溶解性顯著 地下降。 實例B-2(主步驟+後步驟中滴加的Uc中所含有的單 體合計量：2.68質量％)中所獲得的聚合物與比較例b-3 (全部以固定的比例滴加）中所獲得的聚合物相比，溶解 性顯著地提幵’且製成抗餘劑組成物時的感光度提昇。 171 201222146 [表 21] Mw Mw/Mn _____評價結果 溶解性 f添加庚坑量/wt%l 實例B-3 9700 1.71 — 9.91 7.24 比較例B-4 (參考例B-3 ) 10100 1.83 實例B-4 比較例B-5 (參考例B-4) 12300 1.81 16.32 12400 1.89 12.25 實例B-5 比較例B-6 (參考例B-5) · . _ —— — 11600 1.75 9.21 11900 1.82 6.88 實例B-6 6500 1.91 3.02 未溶解於PGMEA 中 比較例B-7 (參考例B-6) 6700 1.93 根據表21的結果，實例B-3 (主步驟+後步驟中滴加 的Uc中所含有的單體合計量：丨.99質量％)中所獲得的聚 合物與比較例B-4 (無主步驟、後步驟的區別而全部以固 定的比例滴加）中所獲得的聚合物相比，溶解性顯著地提 昇。 實例B-4〜實例B-6亦同樣地，藉由聚合反應所生成 的聚合物的組成比於全部反應期間内成為固定的組成比， 可抑制共聚合組成偏差較大的成分的生成。進而，與比較 例B-5〜比較例B_7(無主步驟、後步驟的區別而全部以固 定的比例滴加）中所獲得的聚合物相比，溶解性顯著地提 昇。 以下的例是關於利用本實施形態的共聚合物評價方法 的基於鏈結構的無規性的特性評價的例。但是，本實施形 172 201222146 nu^oopif 態並不限定於該些共聚合物的評價。 &lt;合成例C-1 :均聚物C-A-l&gt; 首先’將3·40份的單體（心丨彡及丨.38份的二曱基-2,2，-偶氮雙異丁酸酯（和光純藥工業公司製造，V601(商品名）） 與I3·6份的乳酸乙醋一同加入至25 mL的舒倫克燒槪中 後，以200 mL/分向溶液内吹入氮氣丨分鐘。繼而，將該 燒瓶置於80°C的水浴上，一邊攪拌一邊攪拌3小時。The resulting polymer (IV) contains the monomer unit _ (poly (four) sister. The results are shown in Figure 17. The ratio is, and is proportional). Comparing with the results of Fig. η, in the reference example μ (Fig. 16), the difference in the polymer composition ratio of the polymer formed at the initial stage of the main step and the target composition was large. In addition, the (tetra) compound, the polymer composition ratio and the target composition are formed from the reaction time of 4 hours from the end of the main step (the end of the dropping liquid) to the reaction time of 7 hours as the end of the holding step. The difference becomes larger as time passes. On the other hand, in the main example, in the main step, Sa is used to design the monomer composition by the above factor, and Tb of the target composition is used, and the supply is set after the end of the main step (the end of the dropwise addition of Tb). A total of 2 hours of the subsequent step of Uc, whereby in the main step, a polymer molecule having a composition substantially the same as the target composition is generated from the beginning of the polymerization reaction, and the state continues, at the end of the main step (reaction time 4 hours) After that, the polymer composition ratio also showed a value very close to the target composition, and the deviation of the composition ratio caused by the reaction time was improved. [Refining of the polymer] 169 201222146 -τν/^, υυ^ιχ In addition to the mixed solvent of decyl alcohol and water used in the purification step of the polymer of Example Β-1 (methanol/water = 80/20 capacity ratio) And (methanol/water = 90/10 volume ratio) was changed to isopropyl ether, and polymer oxime 6 was obtained from the polymerization reaction solution in the flask which had passed the reaction time of 7 hours in the same manner as Example Β-1. The Mw and Mw/Mn of the polymer crucible 6 and the results of solubility evaluation are shown in Table 21. &lt;Comparative Example B-2 to Comparative Example B-7 &gt; In Reference Example to Reference Example B-6, the flask obtained after the reaction was allowed to stand for 7 hours and then cooled to room temperature to stop the reaction was used. The polymerization reaction solution, Reference Example 1 was obtained in the same manner as the purification step of the polymer of the example, and Comparative Example 2 was obtained in the same manner as the purification step of the polymer of Example Β-2. Reference Example-3 A comparative polymer was obtained in the same manner as the purification step of the polymer of Example Β3, and a comparative polymer was obtained in the same manner as in the purification step of the polymer of Example Β4, with reference to Example _5. A comparative polymer was obtained in the same manner as the purification step of the polymer of Example Β-5, and a comparative polymer was obtained in the same manner as in the purification step of the polymer of Example -6. With respect to the obtained comparative polymer, Mw and Mw/Mn were determined in the same manner as in the examples, and solubility evaluation was performed. The results of Comparative Example B-2 and Comparative Example B-3 are shown in Table 20, and the results of Comparative Example 2β_4^ Comparative Example B-7 are shown in Table 21. Further, in Comparative Example ^B-2, Comparative Example B-3, a resist &amp; composition was prepared in the same manner as in Example B-1 using the obtained comparative polymer', and the sensitivity was evaluated. The results are not shown in Table 20. 170 201222146 ^tUZQOpif [Table 20] Mw Mw/Mn _______ Solubility [addition of heptane (wt%)] 感光 Sensitivity (mJ/cm2) Example B-1 10500 1.62 14.2___ 1.01 Comparative Example B-1 10700 1.67 ' 10.8 1.72 Comparative Example B-2 (Reference Example B-1) 10600 1.75 ---- ...____ 11.6 1.65 Example B-2~~ 8400 1.58 6.15 0.51 Comparative Example B-3 (Reference Example B-2) 7400 1.65 5.7 0.78 According to the results of Table 20, the polymer obtained in Example B1 (the total amount of monomers contained in uc added in the main step + after the step: 215 mass 0 / 〇) was compared with Comparative Example B-1 (after In the step, the total amount of the monomers contained in the uc added in the step was 14.9 mass%), and the polymer obtained in Comparative Example B-2 (the difference between the main step and the subsequent step was all added in a fixed ratio) was compared. The solubility is remarkably improved, and the sensitivity at the time of making the anti-rice composition is improved. Further, in Comparative Example B-1 in which the total amount of the monomers contained in the solution Uc dropped in the subsequent step was not appropriately controlled, the solubility was remarkably lowered as compared with the example B-1. The polymer obtained in Example B-2 (the total amount of the monomers contained in the Uc added in the main step + the subsequent step: 2.68 mass%) and the comparative example b-3 (all added in a fixed ratio) were Compared with the obtained polymer, the solubility is remarkably improved and the sensitivity at the time of making the anti-reagent composition is improved. 171 201222146 [Table 21] Mw Mw/Mn _____ Evaluation Results Solubility f Addition of heptules/wt%l Example B-3 9700 1.71 — 9.91 7.24 Comparative Example B-4 (Reference Example B-3) 10100 1.83 Example B -4 Comparative Example B-5 (Reference Example B-4) 12300 1.81 16.32 12400 1.89 12.25 Example B-5 Comparative Example B-6 (Reference Example B-5) · . _ —— — 11600 1.75 9.21 11900 1.82 6.88 Example B -6 6500 1.91 3.02 Not dissolved in PGMEA Comparative Example B-7 (Reference Example B-6) 6700 1.93 According to the results in Table 21, Example B-3 (the single contained in the Uc added in the main step + after the step) The solubility of the polymer obtained in the bulk measurement: 99.99 mass%) compared with the polymer obtained in Comparative Example B-4 (all without a main step and a subsequent step, all added in a fixed ratio) Significantly improved. Similarly, in the case of the example B-4 to the example B-6, the composition ratio of the polymer produced by the polymerization reaction becomes a fixed composition ratio in the entire reaction period, and formation of a component having a large variation in the copolymerization composition can be suppressed. Further, the solubility was remarkably improved as compared with the polymer obtained in Comparative Example B-5 to Comparative Example B_7 (all of which were not added in a fixed ratio without the main step and the subsequent step). The following examples are examples of the evaluation of the characteristics of the randomness based on the chain structure by the copolymer evaluation method of the present embodiment. However, the present embodiment 172 201222146 nu^oopif state is not limited to the evaluation of these copolymers. &lt;Synthesis Example C-1: Homopolymer CA-l&gt; First, '3·40 parts of a monomer (heart and 丨. 38 parts of dimercapto-2,2,-azobisisobutyric acid) Ester (manufactured by Wako Pure Chemical Industries, Ltd., V601 (trade name)) was added to 25 mL of Schlenk simmer together with I3·6 parts of ethyl lactic acid, and nitrogen gas was blown into the solution at 200 mL/min. The flask was placed on a water bath at 80 ° C and stirred for 3 hours while stirring.

繼而，一邊攪拌一邊將所獲得的反應溶液滴加至約2〇 倍量的曱醇中，獲得白色的析出物（均聚物匕A—〗）的沈 澱。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。於 減壓下以40°C對該共聚合物濕粉進行約40 t 得白色粉體（2.0 g)。 、υ,、又 &lt;合成例C-2〜合成例C_3 :均聚物C-A&gt;_2、均聚物 C-A-3 &gt; ” 於本合成例中，除將所使用的單體自上塊（瓜_1)分 別變更為上述（m-2)、上述（m-3)以外，以與人成例^ 相同的操作獲得均聚物C_A-2 (2.4g)、均聚物C_A_3 (丄8 g) 0 &lt;合成例C-4〜合成例C-5 :均聚物d4、 C-A-5&gt; &quot; 於本合成例中，除將所使用的單體自上述（瓜-丨）分 別變更為上述（m-4)、上述（m-5)，將溶劑自钆酸乙酯13 6 g變更為乳酸乙酯與PGMEA的混合物（乳酸己醋/p(^MEA = 50/50質量比）以外’以與合成例μ相同的胃操作獲得 173 201222146 均聚物 C-A-4 (2.7 g)、均聚物 C-A-5 ( 1.4 g)。 &lt;合成例C-6 :均聚物C-A-6&gt; 於本合成例中，除將所使用的單體自（m-1)變更為 下述（m-14)，將溶劑自乳酸乙酯13.6 g變更為二曱基曱 醯胺以外，以與合成例C-1相同的操作獲得均聚物C-A-6 (2.7g)〇 [化9]Then, the obtained reaction solution was added dropwise to about 2 Torr of decyl alcohol while stirring to obtain a precipitate of a white precipitate (homopolymer 匕A-). Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer wet powder was subjected to about 40 t at 40 ° C under reduced pressure to obtain a white powder (2.0 g). , υ, and &lt;Synthesis Example C-2 to Synthesis Example C_3: Homopolymer C-A&gt;_2, Homopolymer CA-3 &gt; ” In the present synthesis example, except that the monomer used is from the top The block (guar_1) was changed to the above (m-2) and the above (m-3), and a homopolymer C_A-2 (2.4 g) and a homopolymer C_A_3 were obtained in the same manner as in the human case.丄8 g) 0 &lt;Synthesis Example C-4 to Synthesis Example C-5: Homopolymer d4, CA-5&gt;&quot; In the present synthesis example, except that the monomer used was from the above (Gua-丨) Change to the above (m-4), the above (m-5), and change the solvent from 13 6 g of ethyl citrate to a mixture of ethyl lactate and PGMEA (lactic acid hexane vinegar / p (^MEA = 50/50 mass) In the same manner as in the synthesis example μ, 173 201222146 homopolymer CA-4 (2.7 g) and homopolymer CA-5 (1.4 g) were obtained. &lt;Synthesis Example C-6: homopolymer CA -6&gt; In the present synthesis example, the solvent was changed from (m-1) to the following (m-14), and the solvent was changed from 13.6 g of ethyl lactate to dimercaptoamine. The homopolymer CA-6 (2.7 g) was obtained by the same operation as in Synthesis Example C-1 [Chemical 9]

(m-14) &lt;合成例C-7 :共聚合物C-B-l&gt; [共聚合物的製造] 於本合成例中，藉由部分滴加方式來使單體（m-1)、 單體（m-2)、單體（m-3)進行聚合。所使用的各單體的 合計量的莫耳比為（m-1) : (m-2) : (m-3) =39.0 : 41.3 : 19.7。 於氮氣環境下，將乳酸乙酯79.0份、單體（m-1) 2.72 份、單體（m-2) 4.90份、單體（m-3) 2.02份加入至具備 氮氣導入口、攪拌機、冷凝器、滴液漏斗、及溫度計的燒 瓶中。將燒瓶放入至水浴中，一邊對燒瓶内進行攪拌一邊 174 201222146 W-d8«pif 將水浴的溫度提高至8〇t。 其後，自加入有乳酸乙醋3.6份與二甲基_2， 異丁酸酯（上述的V6G1(商品名））u96份的滴加^雙 j固定速度歷日寺15分鐘向燒瓶内進行滴加，並且自加 单體（m_l) 23.80份、單體（m_2)办情、單體（瓜 16.52份、乳酸乙酯98.06份、二甲基_2,2，_偶氮雙 上上述的麵（商品名））0.643份的滴加裝置，定1 =、時向燒瓶内進行滴加。進而，將8。。。的溫= 繼而…紐拌-邊將燒瓶_聚合反應溶液滴加至 、，、勺1 〇倍量的甲醉及水的混合溶劑（甲醇/水=8_ 中’獲得白色的析出物（共聚合物C_B_1} 里比) 澱濾除，再次投入至與上述相同量&amp; ’將/u (曱酿/皮-糊n w 3 曱轉及水的混合溶劑 ^曱知/水一90/10夺里比）中’ 一邊授摔一邊進行沈 &gt;月洗。鎌’將綠後的沈職除，獲 獲得白色粉體（66.0 g)。 行4後並=GPC對所獲得的白色粉體進 :刀析，並求出絲合物整體的平均單體組成與勤。另 ^卜，利用上衫法評價賴得的絲合物c_b]的溶解 卜將其絲不絲22。科，將絲合物c 合物C-B·2及共聚合物C_B#自的组成中的單體m_i =fsr::3= 耳比、分子量、作為評價值的評 距離L⑻、表稱解性的時間（分鐘）、作為感光度的 175 201222146 曝光量示於表22。 [抗蝕劑組成物的製造] 於上述所獲得的絲合物C_B_1 100份巾混合作 酸產生劑的三苯基疏三氟甲鮮酸鹽2份、及劑 ΡΟΜΕΛ , 〇 慮态進行過濾’而製備抗蝕劑組成物溶液。針對所 二於^2劑組成物，利用上述方法評價感光度。將其結 〈合成例C-8 :共聚合物C-B-2&gt; 由整體if ^ C_7中’事先不將單體加人至燒瓶内，而藉 體的莫耳^、式來合成共聚合物。本合成例中所使用的單 即 為（功-1 ) : (m-2) : (m-3) =40.0 : 40.0 : 20.0。 例c 於氮氣環境下，將乳酸乙酯64.5份加入至與合成 内進行=吨瓶巾。將燒_人至水浴中，—邊對燒瓶 其广一邊將水浴的溫度提高至8〇。〇。 31.36^、’》。自加入有單體㈤）27.20份、單體（m-2) 基-2,2，、偶^體（❿3) 18.88份、乳酸乙酯112.6份、二甲 份的滴；異丁酸醋（上述的(商品名））2.576 加。進而 以固定速度歷時4小時向燒瓶内進行滴 其後’將8〇°C的溫度保持3小時。 (共聚tM與合成例C_7相同的方式獲得白色的析出物 滤除、乾、ML C B 2)的沈殿’進行遽除、清洗、清洗後的 對，知而獲得白色粉體（64.0 g)。 斤獲侍的共聚合物C_B_2進行與合成例C_7相同的 201222146.(m-14) &lt;Synthesis Example C-7: Copolymer CB-1&gt; [Production of Copolymer] In the present synthesis example, monomer (m-1), single was obtained by partial dropping The body (m-2) and the monomer (m-3) are polymerized. The molar ratio of the total amount of each monomer used was (m-1): (m-2): (m-3) = 39.0: 41.3: 19.7. 79.0 parts of ethyl lactate, 2.72 parts of monomer (m-1), 4.90 parts of monomer (m-2), and 2.02 parts of monomer (m-3) were added to a nitrogen inlet, a stirrer, and a nitrogen gas atmosphere. In a flask of a condenser, a dropping funnel, and a thermometer. The flask was placed in a water bath while stirring the inside of the flask. 174 201222146 W-d8 «pif The temperature of the water bath was raised to 8 〇t. Thereafter, 3.6 parts of lactic acid ethyl acetate and dimethyl 2, isobutyrate (V6G1 (trade name)) u96 parts were added dropwise, and the double j fixed speed was carried out in the flask for 15 minutes. Add dropwise, and add monomer (m_l) 23.80 parts, monomer (m_2), monomer (melon 16.52 parts, ethyl lactate 98.06 parts, dimethyl 2, 2, _ azo double on the above Face (trade name) 0.643 parts of the dropping device was set to 1 =, and the inside of the flask was dropped. Furthermore, it will be 8. . . The temperature = then... the mixture is added to the flask, the polymerization solution is added dropwise, and the spoon is mixed with a mixture of water and water (methanol/water = 8_' to obtain white precipitates (copolymerization). The substance C_B_1} 里比) is deionized and re-introduced to the same amount as above & 'will /u (brewed / skin-paste nw 3 曱 turn and water mixed solvent ^ know / water a 90/10 win In the middle of the 'thinking of the sinking, the sinking is carried out. 镰', after the green post, the white powder (66.0 g) is obtained. After row 4 and = GPC, the white powder obtained is: Knife analysis, and find the average monomer composition of the whole filament and the diligence. Another ^ Bu, using the top of the shirt method to evaluate the dissolution of the silk gel c_b] will not be silk 22. Branch, silk The monomer m_i =fsr::3= the ear ratio, the molecular weight, the evaluation distance L (8) as the evaluation value, the time (minutes) for the solution, and the time (minutes) of the solution property of the composition CB·2 and the copolymer C_B# The exposure amount of 175 201222146 as the sensitivity is shown in Table 22. [Production of Resist Composition] The above-obtained linear compound C_B_1 100 parts of the towel was mixed with triphenylphosphorus trifluoride as an acid generator. A resist composition solution was prepared by filtering 2 parts of the formic acid salt and the ruthenium, and the sensitivity was evaluated by the above method for the composition of the two components. -8: Copolymer CB-2&gt; From the whole if ^ C_7, the monomer was not previously added to the flask, and the copolymer was synthesized by the molar formula. The compound used in the synthesis example Single is (work-1): (m-2): (m-3) = 40.0 : 40.0 : 20.0. Example c 64.5 parts of ethyl lactate is added to the synthesis and ton bottle under nitrogen atmosphere The _ people will be washed into the water bath, and the temperature of the water bath will be raised to 8 对 on the wide side of the flask. 31 31.36^, '》. From the monomer (5) added 27.20 parts, monomer (m-2) Base-2, 2, and oxime (❿3) 18.88 parts, 112.6 parts of ethyl lactate, a drop of dimethyl ester; and isobutyric acid vinegar (the above-mentioned (trade name)) 2.576. Further, the inside of the flask was dripped at a fixed speed for 4 hours. Then, the temperature of 8 ° C was maintained for 3 hours. (Copolymerization tM was obtained in the same manner as in Synthesis Example C_7, and white precipitates were removed, dried, and ML C B 2) was removed, washed, and washed, and a white powder (64.0 g) was obtained. The co-polymer C_B_2 obtained by the pound is the same as the synthesis example C_7 201222146.

Huzoopif 測定及評價。將其結果示於表22。 &lt;合成例C-9:共聚合物〇七3&gt; ，，於=中’事先將所有單體及溶劑加入至燒瓶 耳成共聚合物。本例中所使用的單體的莫 耳比為(叫）=4。。：4。。：2()()。的莫 即，將乳酸乙醋15.5份、單體（m-1) 1.36份、單赞 (m-2) 1.57 份、單體（m_3) 〇 94 份、二甲基_2,2,偶錐Huzoopif determination and evaluation. The results are shown in Table 22. &lt;Synthesis Example C-9: Copolymer 〇7 3&gt;, in which all monomers and solvent were previously added to the flask to form a copolymer. The molar ratio of the monomer used in this example was (called) = 4. . :4. . :2()(). That is, 15.5 parts of lactic acid ethyl acetate, 1.36 parts of monomer (m-1), 1.57 parts of mono (m-2), 94 parts of monomer (m_3), dimethyl 2, 2, and even cone

異丁酸醋（上述的v繼（商品名））115份加入至乃^ 的舒倫克燒瓶中後，以2〇0 mL/分向溶液内吹入氮氣j分 鐘。繼而，將該燒瓶置於80°C的水浴上，一邊擾拌一邊^ 拌3小時。 灵 繼而，一邊攪拌一邊將所獲得的反應溶液滴加至約1〇 倍量的甲醇中，獲得白色的析出物（共聚合物C-B-3)的 沈澱。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。 於減壓下以40°C對該共聚合物濕粉進行約40小時乾燥， 獲得白色粉體C- (2.8 g)。 對所獲得的共聚合物C-B·3進行與合成例C-7相同的 測定及評價。將其結果示於表22。 &lt;合成例C-10 :共聚合物C-B-4&gt; 於本合成例中，藉由部分滴加方式來使單體（m-4)、 單體（m-5)、單體（m-3)進行聚合。所使用的各單體的 合計量的莫弄比為（m-4) : (m-5) : (m-3) =35,5 : 34.3 : 30.2。 於氮氣環境下，將乳酸乙醋42.6份、PGMEA 41.5份、 177 201222146 \J \J Λ. 單體（m-4) 2.83 份、單體（m-5) 8.68 份、單體（m_3) 3.52份加入至與合成例C_7相同的燒瓶中。將燒瓶故入至 ^浴中，一邊對燒瓶内進行攪拌一邊將水浴的溫度提高至 其後，自加入有乳酸乙酯6.5份與二曱基·2,2，_偶氮 異丁酸酯（上述的V601 (商品名））2152份的滴加裝置， 以固定速度歷時20分鐘向燒瓶内進行滴加，並且自加入有 單體（m-4) 18.09 份、單體（m-5) 20.83 份、單體（m_3) 21 · 15份、乳酸乙酯38.6份、PGMEA 45· 1份、二曱基_2 2, 偶氮雙異丁酸酯（上述的V601 (商品名））丨435份^^滴加 裝置’以固定速度歷時4小時向燒瓶内進行滴加。進而， 將80°C的溫度保持3小時。 繼而，-邊擾拌-邊將燒瓶内的聚合反應溶液滴加至 約ίο倍量的曱醇及水的混合溶劑（甲醇/水=85/15容量比） 中’獲得白色的析出物（共聚合物C_B_4)的沈澱。將沈 澱滤除，再次投人至與上述相同量的甲醇及水的混合溶劑 、（甲醇/水= 95/5容量比）中，一邊㈣一邊進行沈殿的清 洗。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。於 減壓下以40°C對該共聚合物濕粉進行約4〇小時乾燥，獲 得白色粉體（54.1 g)。 &amp; 對所獲得的共聚合物(：·Β_4進行與合賴C_7相同的 測定及評價。將其結果示於表23。另外，將共聚合物 C-B-4,共聚合物C-B-5及絲合物C_B_6各自的組成中的 單體m-4、單體m-5及單體m_3的莫耳比、分子量、作為 178 201222146 4UZ36plf 評價值的評價距離L ( S )、表示溶解性的時間（分鐘）、作 為感光度的曝光量示於表23。 &lt;合成例C-11 :共聚合物C-B-5&gt; 於合成例C-10中，事先不將單體加入至燒瓶内，而藉 由整體滴加方式來合成共聚合物。本合成例中所使用的單 體的莫耳比為（m-4 ) . ( m-5 ) : ( m-3 ) = 35.0 : 35 0 : 30 〇。 即’於氮氣環境下，將乳酸乙酯54.5份與PGMEA 23 3After 115 parts of isobutyric acid vinegar (v described above (trade name)) was added to a Schlenk flask, the nitrogen gas was blown into the solution at 2 〇 0 mL/min for 5 minutes. Then, the flask was placed on a water bath at 80 ° C, and mixed while stirring for 3 hours. Further, the obtained reaction solution was added dropwise to about 1 Torr of methanol while stirring to obtain a precipitate of a white precipitate (copolymer C-B-3). Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer wet powder was dried at 40 ° C under reduced pressure for about 40 hours to obtain a white powder C- (2.8 g). The obtained copolymer C-B·3 was subjected to the same measurement and evaluation as in Synthesis Example C-7. The results are shown in Table 22. &lt;Synthesis Example C-10: Copolymer CB-4&gt; In the present synthesis example, a monomer (m-4), a monomer (m-5), and a monomer (m-) were partially added dropwise. 3) Perform polymerization. The molar ratio of the total amount of each monomer used was (m-4): (m-5): (m-3) = 35, 5: 34.3: 30.2. Under nitrogen atmosphere, 42.6 parts of lactic acid ethyl acetate, 41.5 parts of PGMEA, 177 201222146 \J \J Λ. 2.83 parts of monomer (m-4), 8.68 parts of monomer (m-5), monomer (m_3) 3.52 The fraction was added to the same flask as in Synthesis Example C-7. The flask was placed in a bath, and the temperature of the water bath was increased while stirring the inside of the flask, and 6.5 parts of ethyl lactate and dinonyl·2,2,-azoisobutyrate were added thereto. The above-mentioned V601 (trade name) 2152 parts dropping device was dropped into the flask at a fixed speed for 20 minutes, and monomer (m-4) was added to 18.09 parts, and monomer (m-5) 20.83 was added. Parts, monomer (m_3) 21 · 15 parts, ethyl lactate 38.6 parts, PGMEA 45 · 1 part, dimercapto 2 2, azobis isobutyrate (V601 (trade name) above) 丨 435 parts The ^^ dropping device was dropped into the flask at a fixed speed for 4 hours. Further, the temperature at 80 ° C was maintained for 3 hours. Then, while stirring, the polymerization solution in the flask was added dropwise to a mixed solvent of methanol and water (methanol/water = 85/15 capacity ratio) to obtain white precipitates (total Precipitation of polymer C_B_4). The precipitate was filtered off, and the mixture was again poured into a mixed solvent of methanol and water (methanol/water = 95/5 capacity ratio) as described above, and the chamber was cleaned while being (four). Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer wet powder was dried at 40 ° C under reduced pressure for about 4 hours to obtain a white powder (54.1 g). &amp; The obtained copolymer (:·Β_4 was subjected to the same measurement and evaluation as that of C_7. The results are shown in Table 23. In addition, the copolymer CB-4, the copolymer CB-5 and the silk were used. The molar ratio of the monomer m-4, the monomer m-5 and the monomer m_3 in the respective compositions of the compound C_B_6, the molecular weight, the evaluation distance L (S) as the evaluation value of 178 201222146 4UZ36plf, and the time indicating solubility ( Minutes), the exposure amount as the sensitivity is shown in Table 23. <Synthesis Example C-11: Copolymer CB-5> In Synthesis Example C-10, the monomer was not added to the flask in advance, but by The total amount of the monomer was used to synthesize the copolymer. The molar ratio of the monomer used in the present synthesis example was (m-4). (m-5) : (m-3) = 35.0: 35 0 : 30 〇. That is, '54.5 parts of ethyl lactate and PGMEA 23 3 under nitrogen atmosphere

份加入至與合成例C-7相同的燒瓶中。將燒瓶放入至水浴 中，一邊對燒瓶内進行攪拌一邊將水浴的溫度 8〇〇C。 繼而:自加入有單體U-4) 5L17份、單體（m_5) 37.32 份、單體（m_3 ) 3〇 β ^ U.44伤、礼酸乙酯98.0份、PGME, 瓶内進行滴加。進而，以固定速度歷時4小日_ 然後，以與合成例的溫度保持3小時。 (共聚合物C-B-5) · α相同的方式獲得白色的析出净 滤除、乾燥而獲得白色進行滤除、清洗、㊉先後* 對所獲得的共聚合‘c』5l.〇g)。 測定及評價。將豆杜果—進行與合成例C_7相同合 &lt;合成例心:=23。 於合成例C-10中，搴:物⑽6〉 内，並藉由批量方式來A、將所有單體及溶劑加入至燒痛 的單體的莫耳比為（m °成共聚合物。本合成例中所使用 ' )·· (m-5) : (m-3) =36.0 : 32·0 ·· 179 201222146 32.0。 即，將乳酸乙_ 4.9份、PGMEA4.9份、單體（m-4) 1.84 份、單體（m-5) 2.38 份、單體（m-3) 2.27 份、二曱 基-2,2’-偶氮雙異丁酸酯（上述的V601 (商品名））1.725 份加入至25 mL的舒倫克燒瓶中後，以200 mL/分向溶液 内吹入氮氣1分鐘。繼而，將該燒瓶置於80°C的水浴上， 一邊攪拌一邊攪拌3小時。 繼而’一邊授捧一邊將所獲得的反應溶液滴加至約1Q 倍量的曱醇中，獲得白色的析出物（共聚合物C-B-6)的 沈澱。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。 於減壓下以40°C對該共聚合物濕粉進行約40小時乾燥， 獲得白色粉體（6.1 g)。 對所獲得的共聚合物C-B-6進行與合成例C-7相同的 測定及評價。將其結果示於表23。 &lt;合成例C-13 :共聚合物C-B-7&gt; 於本合成例中’藉由事先不將單體加入至燒瓶内而進 行聚合的方法（整體滴加方式）來合成單體（U^l)、單體 (m-14)、單體（m-3)。所使用的各單體的合計量的莫耳 比為（m-1 ) : (m-14) : (m-3) =40.0 : 40.0 : 20.〇。 即’於氮氣環境下，將DMF 43.1份加入至與合成例 C-7相同的燒瓶中。將燒瓶放入至水浴中，一邊對燒瓶内 進行攪拌一邊將水浴的溫度提高至80。(：。 其後，自加入有單體（m-1 ) 10.21份、單體（m_14) 8.53 份、單體（m-3 ) 7.09 份、DMF 60.3 份、二曱基-2 2、 180 201222146 HUZOOpif 偶氮雙異丁酸酯（上述的V601 (商品名））0449份的滴加 裝置，以固定速度歷時3小時向燒瓶内進行滴加。進 將80°C的溫度保持3小時。 ’ 繼而，一邊攪拌一邊將燒瓶内的聚合反應溶液滴加至 約1 〇倍量的曱醇及水的混合溶劑（曱醇/水=70/30容量比） 中，獲得白色的析出物（共聚合物C_B_7)的沈澱。將沈 炎濾除，再次投入至與上述相同量的曱醇及水的混合溶劑 • (曱醇/水二70/30容量比）中，一邊攪拌一邊進行沈澱的 清洗。然後，將清洗後的沈澱濾除，獲得共聚合物濕粉。 於減壓下以40 C對該共聚合物濕粉進行約40小時乾燥， 獲得白色粉體（20.1 g)。 對所獲得的共聚合物C-B-7進行與合成例C-7相同的 測定及評價。將其結果示於表24。另外，將聚合物C-B-7 及聚合物C-B-8各自的組成中的單體、單體m_i4及單 體m-3的莫耳比、分子量、作為評價值的評價距離l(s)、 表示溶解性的時間（分鐘）、作為感光度的曝光量示於表 • 24。 &lt;合成例C-14 :共聚合物c_B-8&gt; 於合成例C-13中’事先將所有單體及溶劑加入至燒瓶 内，並藉由批量方式來合成共聚合物。本合成例中所使用 的早體的莫耳比為（m_l ) : (m-14) : (m-3 )二4〇.〇 : 40.0 : 20.0。 即，將DMF 8.3份、單體（m」）〇 82份、單體（m-14) 0.68份、單體（m_3) 0.57份、二甲基_2,2，_偶氮雙異丁酸 181 201222146 酯（上述的V601 (商品名））0.332份加入至25 mL的舒 儉克燒瓶中後，以200 mL/分向溶液内吹入氮氣1分鐘。 繼而’將該燒瓶置於80°C的水浴上，一邊攪拌一邊擾摔6 小時。 繼而，一邊攪拌一邊將所獲得的反應溶液滴加至約1〇 倍量的甲醇及水的混合溶劑（甲醇/水= 80/20容量比）中， 獲得白色的析出物（共聚合物C-B-8)的沈殿。然後，將 清洗後的沈澱濾除，獲得共聚合物濕粉。於減壓下以4〇它 對該共聚合物濕粉進行約40小時乾燥，獲得白色粉體（i 5 g)。 對所獲得的共聚合物C-B-8進行與合成例c_7相同每 測定及評價。將其結果示於表24 ^ 、 &lt;應用例C-l&gt; 於NMR測定部350 +分別進行合· CM〜合❹ C-3中所獲得的均聚物C-A]〜均聚物c_a_3、合成例c·, 2成例09中所獲得的共聚合物C 〜共聚合物c_B_, 的合計6種聚合物的nC_NMR測定。 ^ NMR則定部350中，獲得各樣品的NMR矢 350將測定時的累計次數設為邏 甲基亞石風（39.5ppm)，'進^; 14她，將基峰設為二 正，並將所獲得的各樣=丁 Γ測㈣NMR綠的基線杉 出。 ’的FID資料向波形處理部311賴The fraction was added to the same flask as in Synthesis Example C-7. The flask was placed in a water bath, and the temperature of the water bath was 8 ° C while stirring the inside of the flask. Then: from the addition of monomer U-4) 5L17 parts, monomer (m_5) 37.32 parts, monomer (m_3) 3〇β ^ U.44 injury, ethyl oxalate 98.0 parts, PGME, drop in the bottle . Further, it was kept at a fixed speed for 4 hours _ and then kept at the temperature of the synthesis example for 3 hours. (Copolymer C-B-5) • The white precipitate was removed in the same manner as α, and dried to obtain a white color for filtration, washing, and the obtained copolymerization 'c』5l.〇g). Determination and evaluation. Bean Duguo - was combined with Synthesis Example C_7 &lt;Synthesis Example: =23. In Synthesis Example C-10, 搴: (10) 6>, and by mass, A, all monomers and solvent were added to the painful monomer, the molar ratio was (m ° into a copolymer. ' )·· (m-5) used in the synthesis example: (m-3) = 36.0 : 32·0 ·· 179 201222146 32.0. That is, 4.9 parts of lactic acid, 4.9 parts of PGMEA, 1.84 parts of monomer (m-4), 2.38 parts of monomer (m-5), 2.27 parts of monomer (m-3), and dimercapto-2, After adding 1.725 parts of 2'-azobisisobutyrate (V601 (trade name)) described above to a 25 mL Schlenk flask, nitrogen gas was blown into the solution at 200 mL/min for 1 minute. Then, the flask was placed in a water bath at 80 ° C, and stirred for 3 hours while stirring. Then, the obtained reaction solution was added dropwise to about 1Q times of sterol, and a precipitate of a white precipitate (copolymer C-B-6) was obtained. Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer wet powder was dried at 40 ° C under reduced pressure for about 40 hours to obtain a white powder (6.1 g). The obtained copolymer C-B-6 was subjected to the same measurement and evaluation as in Synthesis Example C-7. The results are shown in Table 23. &lt;Synthesis Example C-13: Copolymer CB-7&gt; In the present synthesis example, a monomer (U^ was synthesized by a method in which polymerization was carried out without adding a monomer to a flask in advance (integral dropping method). l), monomer (m-14), monomer (m-3). The molar ratio of the total amount of each monomer used was (m-1) : (m-14) : (m-3) = 40.0 : 40.0 : 20.〇. Namely, 43.1 parts of DMF was added to the same flask as in Synthesis Example C-7 under a nitrogen atmosphere. The flask was placed in a water bath, and the temperature of the water bath was raised to 80 while stirring the flask. (:. Thereafter, 10.21 parts of monomer (m-1), 8.53 parts of monomer (m_14), 7.09 parts of monomer (m-3), 60.3 parts of DMF, 2, 2, 2, 1, 2012, 2012 HUZOOpif azobisisobutyrate (V601 (trade name) above) 0449 parts dropping device was added dropwise to the flask at a fixed speed for 3 hours. The temperature was maintained at 80 ° C for 3 hours. The polymerization reaction solution in the flask was added dropwise to a mixed solvent of decyl alcohol and water (sterol/water = 70/30 volume ratio) while stirring to obtain a white precipitate (copolymer). The precipitate of C_B_7) was filtered off, and the mixture was again added to the same amount of the above-mentioned mixed solvent of decyl alcohol and water (the ratio of the sterol/water ratio of 70/30), and the precipitate was washed while stirring. The washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer wet powder was dried at 40 C under reduced pressure for about 40 hours to obtain a white powder (20.1 g). The polymer CB-7 was subjected to the same measurement and evaluation as in Synthesis Example C-7. The results are shown in Table 24. The molar ratio of the monomer, the monomer m_i4, and the monomer m-3 in the composition of each of the polymer CB-7 and the polymer CB-8, the molecular weight, the evaluation distance l(s) as an evaluation value, and the solubility The time (minutes) and the exposure amount as the sensitivity are shown in Table 24. [Synthesis Example C-14: Copolymer c_B-8&gt; In Synthesis Example C-13, all monomers and solvents were added in advance to The copolymer was synthesized in a batch by batch method. The molar ratio of the early body used in the present synthesis example was (m_l): (m-14): (m-3) two 4 〇. 〇: 40.0 : 20.0. That is, DMF 8.3 parts, monomer (m") 〇 82 parts, monomer (m-14) 0.68 parts, monomer (m_3) 0.57 parts, dimethyl 2, 2, _ azo double After isobutyric acid 181 201222146 ester (V601 (trade name) above) 0.332 parts was added to a 25 mL Schulk flask, nitrogen was blown into the solution at 200 mL/min for 1 minute. Then the flask was placed On a water bath of 80 ° C, the mixture was stirred for 6 hours while stirring. Then, the obtained reaction solution was added dropwise to a mixed solvent of methanol and water (methanol/water = 80/20 capacity) while stirring. In the ratio, a white precipitate (copolymer CB-8) was obtained. Then, the washed precipitate was filtered off to obtain a copolymer wet powder. The copolymer was subjected to 4 Torr under reduced pressure. The wet powder was dried for about 40 hours to obtain a white powder (i 5 g). The obtained copolymer CB-8 was subjected to the same measurement and evaluation as in Synthesis Example c_7. The results are shown in Table 24^, &lt;Application Example C-1&gt; In the NMR measurement unit 350+, the homopolymer CA] to the homopolymer c_a_3 obtained in the combination of CM and hydrazine C-3, respectively, were synthesized. Example c·, 2% of the total of 6 kinds of polymers obtained from the copolymer C to the copolymer c_B_ obtained in Example 09 were measured by nC_NMR. ^ NMR in the fixed portion 350, the NMR vector 350 obtained for each sample is set to the number of times of the measurement, which is set to the logical methyl slate (39.5 ppm), and the peak is set to be positive. Each of the obtained = Γ Γ (4) NMR green baseline cedar. 'The FID data is directed to the waveform processing unit 311

N1VN1V

繼而’波形處理部311自所獲得的nD信號中的 182 201222146 ^wzoopif ==頻率+’以 0.25ppm = Π5 — _的範圍進行積分，而獲得16: 而且’波形處理部311對均聚物C A-卜 幻 如’一):並對應於 存=^=〜_寫人、儲Then, the 'waveform processing section 311 integrates from the range of 0.25 201222146 ^wzoopif == frequency + ' in the obtained nD signal by 0.25 ppm = Π5 - _ to obtain 16: and the 'waveform processing section 311 pairs the homopolymer C A-birth as 'a): and corresponding to save = ^ = ~ _ write people, save

c Β =波形處理部311對共聚合物C-B-i〜共聚合物 庫r予樣品識別資訊（例如，β]〜β·3)，並對 資訊，將各樣品的共聚合物的NMR光譜 抖寫入、儲存於雇R資料儲存部315中。c Β = waveform processing unit 311 gives sample identification information (for example, β] to β·3) to the copolymer CBi to the copolymer library r, and writes the NMR spectrum of the copolymer of each sample to the information. And stored in the hire R data storage unit 315.

Svst繼而^成分分析部312利用例如P咖m Recogmtion 體二由的如仍（註冊商標）作為多變量分析軟 ΙΓΖ，1〜均聚物Μ3及共聚合Μ·1〜 ^自（合計6種聚合物）的NMR光譜資料， 析，二〔二於緩基碳的合計16個積分值的主成分分 .^ 式所示的矩陣G的實驗模型。 置背共聚合物的組成+的單體為3種，故將配 主象勺樣品的主成分空間的維度設為三維，即，將 主成分數設為3個。而a，结， 成分的貢獻率二成分至第3主成分的各 幻成為 673/^24.50/(^7.90/^ 殘渣為 0.5%。 〜聚物〜均聚物C_A·3及共聚合物C-B·1 主I、二 ·Β'3各自的第1主成分（以下，PC1)、第2 成为（以下，PC2)、及第3主成分 (以下，PC3 )的主 183 201222146 成分得分（分數）成為如表25所千 部戰算出的均聚物分析 _〜找合物C_B_3各自的第物 第3主成分各自的域分縣=43分、以主成分及 繼而，數值轉換部313根據圖3所示的包含第！主成 主成分㈣2及第3主成分軸⑽的三維 工，中，轉物C-A-1〜均聚物c_a_3及共聚合物cb iThe Svst and then the component analysis unit 312 uses, for example, P (M), as a multivariate analysis software, 1 to homopolymer Μ3, and copolymerization Μ1 to ^ from (total 6 kinds of polymerizations). The NMR spectrum data of the material, and the experimental model of the matrix G shown by the formula of the main component of the 16 integral values of the sum of the slow-base carbons. Since there are three kinds of monomers having the composition of the back copolymer, the dimension of the principal component space of the sample of the master image is three-dimensional, that is, the number of principal components is three. And the contribution ratio of a, knot, and composition to the third principal component is 673/^24.50/(^7.90/^ residue is 0.5%. ~Polymer~Homopolymer C_A·3 and copolymer CB ·1 main component (hereinafter, PC1) of the main I, the second Β'3, and the main 183 201222146 component score (score) of the second (hereinafter, PC2) and the third principal component (hereinafter, PC3) The homopolymer analysis calculated in Table 25 is a domain division of each of the third principal components of the respective components C_B_3 = 43 minutes, with the main component and then, the numerical value conversion unit 313 according to FIG. The three-dimensional work including the main component of the main component (4) 2 and the third principal component axis (10), the transgene CA-1 to the homopolymer c_a_3 and the copolymer cb i

〜，、聚合物CI3各自的座標值（由各_主成分得分所 不的主成分空間中的位置），算出自均聚物cw〜均聚物 C-A-3所形成的二維空間（二維平面）至聚合物π]〜 聚合物C-B-3各自的座標為止的評價距離L⑻。〜, and the coordinate value of each of the polymer CI3 (the position in the principal component space which is not included in each _ principal component score), and the two-dimensional space formed from the homopolymer cw to the homopolymer CA-3 is calculated (two-dimensional space) Evaluation distance L (8) from the plane) to the coordinates of each of the polymer π] to the polymer CB-3.

此處，數值轉換部313分別使用帛！主成分軸pci的 座標值PCI (X)、第2主成分軸PC2的座標值pC2 (χ) 及第3主成分軸PC3的座標值pC3 (χ)這三者，如下述 般表不作為三維空間的主成分空間中的均聚物C A i、均 聚物C-A-2、均聚物C-A-3、及共聚合物C_B_卜共聚合物 C-B-2、共聚合物C-B-3各自的座標點。另外，座標值中的 ()内的X是表示評價對象的共聚合物的樣品的樣品識別 資訊。 均聚物C-A-1的座標值： P (A-l) = (PCI (Α-1) ,ρ〇2 (A-l) , PC3 (A-1)) 均聚物C-A-2的座標值： P (A-2) = (PCI (A-2) ,PC2 (A-2) , PC3 (A-2)) 184 201222146 HU/,0〇pif 均聚物C-A-3的座標值： P (A-3) = (PCI (A-3) ,PC2 (A-3) , PC3 (A-3)) 共聚合物C-B-l的座標值： P (B-l) = (PCI (B-l) ,PC2 (B-l)，PC3 (B-l)) 共聚合物C-B-2的座標值： P (B-2) = (PCI (B-2)，PC2 (B-2)，PC3 (B-2)) 共聚合物C-B-3的座標值： P (B-3) = (PCI (B-3) ,PC2 (B-3) , PC3 (B-3)) 此處，均聚物C-A-l、均聚物C-A-2、均聚物C-A-3 是於聚合物鏈中，作為單一的構成單元的單體完全連續地 配置並鍵結。因此，通過座標值P(A-l)、座標值P(A-2)、 座標值P (A-3)這三者的二維平面（二維的比較空間）是 形成有構成單元的單體的連續性最高，換言之無規性最小 的共聚合物的集合的比三維空間的主成分空間少1個維度 的二維空間。因此，如已說明般，自該二維平面至評價對 象的共聚合物為止的評價距離L(S)是自顯示無規性最少 的性質的二維平面的距離，表示共聚合物中的鏈中的單體 的配置的無規性。 然後，數值轉換部313如下式般求出數值a、數值b、 185 201222146 數值c、數值d。 a- (PC2 (A-2) -PC2 (A-l)) x (PC3 (A-3) -PC3 (A-1)) - (PC2 (A-3) -PC2 (A-l)) x (PC3 (A-2) -PC3 (A-l)) b= (PC3 (A-2) -PC3 (A-l)) x (PCI (A-3) -PCI (A-l)) - (PC3 (A-3) -PC3 (A-l)) x (PCI (A-2) -PCI (A-l)) c= (PCI (A-2) -PCI (A-l)) x (PC2 (A-3) -PC2 (A-l)) - (PCI (A-3) -PCI (A-l)) x (PC2 (A-2) -PC2 (A-l )) d = - (PC2 (A-2) -PC2 (A-l)) x (PC3 (A-3) -PC3 (A-l)) - (PC2 (A-3) -PC2 (A-l)) χ (PC3 (A-2) -PC3 (A-l)) xPCl (A-l) - (PC3 (A-2) -PC3 (A-l)) x (PCI (A-3) -PCI (A-l)) - (PC3 (A-3) -PC3 (A-l)) χ (PCI (A-2 ) -PCI ( A-l )) xPCl ( A-2 ) - ( PCI ( A-2 ) -PCI ( A-l )) χ (PC2 (A-3) -PC2 (A-l)) - (PCI (A-3) -PCI (A-l)) x (PC2 (A-2) -PC2 (A-l)) xPCl (A-3) 繼而’數值轉換部313使用所求出的數值a、數值b 及數值c’藉由以下的式而算出通過座標點p ( a_i )、座 186 201222146 HU^OOpif ϋ P (A_2)、座標點p (A_3)的全部3點的二維平面與 &quot;平貝對象的共聚合物的座標點p (pci，pc2, p 距離L· (s)。 1 1貝 L- I axSPCl + bxSPC2 + cxSPC3 + d | / (a2 + b2 + 八純^式中’ SPC1為評價對象的共聚合物的第1主成 ^象！!座標值（第1主成分的主成分得分），spc2為評 分得分），SPC3為評價對象的==== 成刀f中的座標值（第3主成分社成分得分）。 主;般，將表示評價對象的絲合物的特性的於 主成刀二間中的位置的座標點Here, the numerical value conversion unit 313 uses 帛! The coordinate value PCI (X) of the principal component axis pci, the coordinate value pC2 (χ) of the second principal component axis PC2, and the coordinate value pC3 (χ) of the third principal component axis PC3 are expressed as three-dimensional space as follows. The coordinate points of the homopolymer CA i , the homopolymer CA-2, the homopolymer CA-3, and the copolymer C_B_bu copolymer CB-2 and the copolymer CB-3 in the main component space . Further, X in () of the coordinate value is sample identification information indicating a sample of the copolymer of the evaluation target. Coordinate values of homopolymer CA-1: P (Al) = (PCI (Α-1) , ρ〇2 (Al) , PC3 (A-1)) Coordinate value of homopolymer CA-2: P (A -2) = (PCI (A-2), PC2 (A-2), PC3 (A-2)) 184 201222146 HU/,0〇pif Homogene CA-3 Coordinates: P (A-3) = (PCI (A-3) , PC2 (A-3) , PC3 (A-3)) Coordinate values of the copolymer CBl: P (Bl) = (PCI (Bl) , PC2 (Bl), PC3 (Bl )) Coordinate value of copolymer CB-2: P (B-2) = (PCI (B-2), PC2 (B-2), PC3 (B-2)) Coordinate value of copolymer CB-3 : P (B-3) = (PCI (B-3) , PC2 (B-3) , PC3 (B-3)) Here, homopolymer CA1, homopolymer CA-2, homopolymer CA- 3 is that in the polymer chain, the monomer as a single constituent unit is completely continuously arranged and bonded. Therefore, the two-dimensional plane (two-dimensional comparison space) of the three values of the coordinate value P (Al), the coordinate value P (A-2), and the coordinate value P (A-3) is a single body in which the constituent unit is formed. The two-dimensional space with the highest continuity, in other words, the smallest random group of copolymers, is less than one dimension of the principal component space of the three-dimensional space. Therefore, as already explained, the evaluation distance L(S) from the two-dimensional plane to the copolymer of the evaluation object is the distance from the two-dimensional plane showing the property of least randomness, indicating the chain in the copolymer. The randomness of the configuration of the monomers. Then, the numerical value conversion unit 313 obtains the numerical value a, the numerical value b, and the 185 201222146 numerical value c and the numerical value d as follows. A- (PC2 (A-2) -PC2 (Al)) x (PC3 (A-3) -PC3 (A-1)) - (PC2 (A-3) -PC2 (Al)) x (PC3 (A -2) -PC3 (Al)) b= (PC3 (A-2) -PC3 (Al)) x (PCI (A-3) -PCI (Al)) - (PC3 (A-3) -PC3 (Al )) x (PCI (A-2) -PCI (Al)) c= (PCI (A-2) -PCI (Al)) x (PC2 (A-3) -PC2 (Al)) - (PCI (A -3) -PCI (Al)) x (PC2 (A-2) -PC2 (Al )) d = - (PC2 (A-2) -PC2 (Al)) x (PC3 (A-3) -PC3 ( Al)) - (PC2 (A-3) - PC2 (Al)) χ (PC3 (A-2) - PC3 (Al)) xPCl (Al) - (PC3 (A-2) - PC3 (Al)) x (PCI (A-3) - PCI (Al)) - (PC3 (A-3) - PC3 (Al)) χ (PCI (A-2) - PCI (Al )) xPCl ( A-2 ) - (PCI (A-2) -PCI ( Al )) χ (PC2 (A-3) - PC2 (Al)) - (PCI (A-3) - PCI (Al)) x (PC2 (A-2) - PC2 ( Al)) xPC1 (A-3) Then, the numerical value conversion unit 313 calculates the passing coordinate point p (a_i) and the seat 186 201222146 HU^OOpif using the obtained numerical value a, the numerical value b, and the numerical value c' by the following equation. ϋ P (A_2), the coordinate point p (A_3), the two-dimensional plane of the three points and the coordinate point p of the copolymer of the &quot;pine object (pci, pc2, p distance L·(s). 1 1 shell L - I axSPCl + bxSPC2 + cxSPC3 + d | / (a2 + In the b2 + 八纯^式, 'SPC1 is the first main image of the co-polymer to be evaluated!! Coordinate value (principal component score of the first principal component), spc2 is the scoring score), and SPC3 is the evaluation target = === Coordinate value in the knives f (the third principal component community component score). Mainly, the coordinate point of the position in the main knives of the main knives indicating the characteristics of the evaluated stitches

3種單體的各單體的咐物的 ⑽、座標點Ρ==點：⑷)、座標點P Λ 绝3點的二維平面的評價距離L 撼士 丁#1人2如根據表22可知般，評價距離L(S) 越大Ί鏈的無規性越高， 的微影製程特性越良好。 附及對於九⑽先度 如根據表22可知般，評價距離 =3、共聚合物叫、共聚合物咖的順序變H ^使用4/、聚5物所製備的抗餘劑用組成物的溶解性及 ^光的感光度的微影製程特性伴隨評價距離L(S)按共 4 a物C-B-3、共聚合物C_B 2、共聚合物c b i的順序變 187 201222146 2提^因此’製備用作抗_的抗_用组成物，即 便不貫際進行《彡脉’藉纟求_則心㈣ 製備的共聚合物的評價距離L⑻，亦可推斷自該=聚合 物所製備的抗賴肋成物的微f彡製料性。此處了丘^ 合物C-B_3對於光的感光度低至無法進行測定的程戶= 溶解性亦未於可測定的時間内完全地溶解。 又 &lt;應用例C-2 &gt; 刀別進订合成例C-3〜合成例c_5中所獲得的均聚物 C-A-3〜均聚物C_A_5、合成例c_1〇〜合賴c i2中所獲 得的共聚合物C-B-4〜共聚合物C_B_6的合計6種聚合物 的C-NMR測定，而獲得光譜。再者，將測定時的累計次 數設為5000次，將FID處理時的擴張因數設為4 〇 Hz， 將基峰设為二曱基亞;ε風（39.5 ppm)，進行基線校正。 繼而，自所獲得的各個光譜中，以〇 25 ppm的間隔對 源自聚合物的羰基碳的173 ppm〜179 ppm的範圍進行積 分’而獲得20個積分值。 與應用例C-1同様地求出主成分得分、自通過包含關 於所有均聚物的主成分得分的點的平面的評價距離L(s)。 將表示第1主成分軸PCI、第2主成分軸PC2、及第 3主成分軸PC3各自的座標值的各主成分的主成分得分 (分數）示於表26’將評價距離l(s)的結果示於表23。 另外，將主成分分析部312所算出的均聚物C-A-3〜均聚 物C-A-5及共聚合物C-B-4〜共聚合物c-B-6各自的第1 主成分、第2主成分及第3主成分各自的主成分得分示於 201222146 ^υζβδριί 表26。 c β ^ 可知般’評價距離l⑻是按共聚合物(10), coordinate point Ρ == point: (4)) of each monomer of the three kinds of monomers, and the evaluation distance of the two-dimensional plane of the coordinate point P 绝 by 3 points 撼士丁#1人2 according to Table 22 It can be seen that the higher the evaluation distance L(S), the higher the randomness of the Ί chain, and the better the lithography process characteristics. As for the composition of the anti-reagent prepared by the evaluation of the distance = 3, the order of the copolymer, the co-polymer coffee, and the use of 4/, poly 5, for the nine (10) first degree, as shown in Table 22 The lithography process characteristics of the solubility and the sensitivity of the light are accompanied by the evaluation distance L(S) in the order of a total of 4 a CB-3, a copolymer C_B 2, a copolymer cbi 187 201222146 2 As the anti-composition composition of anti-_, even if the evaluation distance L(8) of the copolymer prepared by "Ximai" is satisfied, the anti-laid prepared from the polymer can be inferred. The micro-f彡 material properties of the ribs. Here, the sensitivity of the mauve C-B_3 to light is so low that it cannot be measured. The solubility is not completely dissolved in a measurable time. Further, &lt;Application Example C-2 &gt; The homopolymer CA-3 to the homopolymer C_A_5 obtained in Synthesis Example C-3 to Synthesis Example c_5, and the synthesis example c_1〇~合赖 c i2 A spectrum was obtained by C-NMR measurement of a total of 6 polymers of the obtained copolymer CB-4 to copolymer C_B_6. Further, the cumulative number of times of measurement was set to 5000 times, the expansion factor at the time of FID treatment was set to 4 〇 Hz, the base peak was set to diterpene base, and the ε wind (39.5 ppm) was used for baseline correction. Then, from the respective spectra obtained, the range of 173 ppm to 179 ppm of the carbonyl carbon derived from the polymer was integrated at intervals of 〇 25 ppm to obtain 20 integral values. In the same manner as in the application example C-1, the principal component score and the evaluation distance L(s) from the plane passing through the point including the principal component scores of all the homopolymers were obtained. The principal component score (score) of each principal component indicating the coordinate value of each of the first principal component axis PCI, the second principal component axis PC2, and the third principal component axis PC3 is shown in Table 26', and the evaluation distance l(s) is shown. The results are shown in Table 23. Further, the first main component and the second main component of each of the homopolymer CA-3 to the homopolymer CA-5 and the copolymer CB-4 to the copolymer cB-6 calculated by the main component analysis unit 312 and The principal component scores of the third principal component are shown in 201222146^υζβδριί Table 26. c β ^ knows that the evaluation distance l (8) is based on the copolymer

如、共聚合物化4的順序變長，且 :+於去二2 ♦合物所製備的抗_用組成物的溶解性及 你pL、度的微影製程特性伴隨評價距離[⑻按共 二钽Θ 6、共聚合物C-B-5、共聚合物C-B-4的順序變 μ杳幵、因此’製備用作抗姓劑的抗餘劑用組成物，即 制進仃微影製程’藉由求出驗抗㈣用組成物的 ㈣評價轉L(s)，亦可麟自該共聚合 •備軌_驗成物的微難程齡。此處，共聚 :勿（：·Β·6對於細感光度低至無法進行測定的程度且 溶解性亦未於可測定的時_完全地溶解。 &lt;應用例C-3 &gt; ye刀別進行合成例C-：l、合成例C-3、合成例C-6中所獲 得的均聚物C-A-1、均聚物C_A_3、均聚物。八_6，合成例 c -13〜合成例c -14中所獲得的共聚合物c _ B _ 7及共聚合物 C-B-8的合計5種聚合物的i3c_NMR測定，而獲得光譜。 再者，將測定時的累計次數設為5〇〇()次，將nD處理時 的擴張因數設為3.0 Hz，將基峰設為二甲基亞颯（39·5 ppm)，進行基線校正。 繼而，如已說明般，自各聚合物的各個NMR光譜信 號中’以0.25 ppm的間隔對源自聚合物的羰基碳的174 ppm〜179 ppm的範圍進行積分，而獲得16個積分值。 與應用例C-1同樣地，進行根據NMR光譜信號所求 189 201222146 出的NMR光譜資料的主成分分析，求出主成分得分、自 通過包含關於所有均聚物的主成分得分的點的平面的評價 距離L (S)。For example, the order of co-polymerization 4 becomes longer, and: the solubility of the anti-composition composition prepared by +2 to the de- 2 ♦ compound and the lithographic process characteristics of your pL and degree are accompanied by the evaluation distance [(8) according to the total two钽Θ 6, the order of the copolymer CB-5, the copolymer CB-4 becomes μ杳幵, thus 'preparing the composition for the anti-surplus agent used as an anti-surname agent, that is, the process of making the lithography process' Find the (4) evaluation of the composition of the test resistance (4) and transfer the L(s). It can also be obtained from the co-polymerization and preparation of the track. Here, the copolymerization: Do not completely dissolve the fine sensitivity to such an extent that the measurement cannot be performed and the solubility is not measurable. <Application Example C-3 &gt; ye knife The homopolymer CA-1, the homopolymer C_A_3, and the homopolymer obtained in Synthesis Example C-: 1, Synthesis Example C-3, Synthesis Example C-6 were carried out. Octa-6, Synthesis Example c-13 to Synthesis The i3c_NMR measurement of the total of the five polymers of the copolymer c_B_7 and the copolymer CB-8 obtained in Example c-14 was carried out to obtain a spectrum. Further, the cumulative number of times in the measurement was set to 5〇. 〇() times, the expansion factor at the time of nD treatment was set to 3.0 Hz, and the base peak was set to dimethyl sulfoxide (39·5 ppm) to perform baseline correction. Then, as explained, each of the respective polymers was used. In the NMR spectrum signal, the range of 174 ppm to 179 ppm of the carbonyl carbon derived from the polymer was integrated at intervals of 0.25 ppm to obtain 16 integral values. In the same manner as in Application Example C-1, the signal according to NMR spectrum was performed. The principal component analysis of the NMR spectrum data obtained from 189 201222146 was obtained, and the principal component score was obtained, and the self-contained component containing all the homopolymers was obtained. Evaluation point plane distance L (S).

將表示第1主成分軸PC1、第2主成分軸PC2、及第 3主成分軸PC3各自的座標值的各主成分的主成分得分 (分數）示於表27，將評價距離L(S)的結果示於表24。 另外，將主成分分析部312所算出的均聚物c-A-1、均聚 物C-A-3及均聚物C-A-6以及共聚合物c_B-7及共聚合物 C-B-8各自的第i主成分、第2主成分及第3主成分各自 的主成分得分示於表27。The principal component score (score) of each principal component indicating the coordinate value of each of the first principal component axis PC1, the second principal component axis PC2, and the third principal component axis PC3 is shown in Table 27, and the evaluation distance L(S) is shown. The results are shown in Table 24. Further, the i-th main of each of the homopolymer cA-1, the homopolymer CA-3, the homopolymer CA-6, the copolymer c_B-7, and the copolymer CB-8 calculated by the principal component analysis unit 312 The main component scores of each of the component, the second principal component, and the third principal component are shown in Table 27.

如根據表24可知般’評價距離l (s)是按共聚合物 C B-8、共聚合物c_B_7的順序變長，且可知使用該共聚告 物所製備的抗# _組成㈣溶解性及躲光的感光度的 ^製程特鱗隨評價距離L⑻按共聚合物C-B-8、共 二口物C-B-7的順序變長而提昇。因此，製備用作抗蝕劑 =飾劑用組成物，即便不實際進行微影製程，藉由求出 (亢姓齊丨用組成物的製備的共聚合物的評價距離[ 微影製=斷自該共聚合物所製備的抗轴 劑用組成物的 190 201222146As can be seen from Table 24, the evaluation distance l (s) is lengthened in the order of the copolymer C B-8 and the copolymer c_B_7, and it is known that the anti-# composition (IV) solubility prepared by using the copolymer is The sensitivity of the light-receiving sensitivity scale is increased as the evaluation distance L(8) becomes longer in the order of the copolymer CB-8 and the two-part CB-7. Therefore, it is prepared as a composition for a resist = a decorative agent, and even if the lithography process is not actually performed, the evaluation distance of the copolymer prepared by the composition of the surname is obtained. [Micro-shadow = broken The composition for the anti-axis agent prepared from the copolymer 190 201222146

感光度 (mJ/cm2) 1.32 1.61 無法評價 溶解性 (分鐘） 卜 未完全溶解 L (S) 19.5 19.1 18.5 分子量 Mw 10000 10600 10000 平均單體組成（莫耳％) HAdMA (m-3) Os 〇 (N 寸 »—Η ECHMA(m-2) 寸 as m Ο α-GBLMA (m-1) 〇 聚合物 C-B-l C-B-2 C-B-3 鬥 e(N&lt;】 感光度 (mJ/cm2 ) 0.54 0.78 無法評價 溶解性 (分鐘） (N oo 未完全溶解 L (S) 17.3 15.7 分子量 Mw 8200 6900 7500 平均單體組成（莫耳％) HAdMA (m-3) m 〇 m OO (N EAdMA (m-5) (N m co HGBMA (m-4) 卜 cn 卜 m 聚合物 C-B-4 C-B-5 C-B-6 201222146 J'asooCNo 寸Sensitivity (mJ/cm2) 1.32 1.61 Unable to evaluate solubility (minutes) Bu not completely dissolved L (S) 19.5 19.1 18.5 Molecular weight Mw 10000 10600 10000 Average monomer composition (mol%) HAdMA (m-3) Os 〇 ( N inch»—Η ECHMA(m-2) inch as m Ο α-GBLMA (m-1) 〇 polymer CBl CB-2 CB-3 bucket e (N&lt;] sensitivity (mJ/cm2) 0.54 0.78 cannot be evaluated Solubility (minutes) (N oo not completely dissolved L (S) 17.3 15.7 Molecular weight Mw 8200 6900 7500 Average monomer composition (mol %) HAdMA (m-3) m 〇m OO (N EAdMA (m-5) ( N m co HGBMA (m-4) 卜 cn 卜 m polymer CB-4 CB-5 CB-6 201222146 J'asooCNo inch

【寸&lt;N&lt;t_—I 感光度 (mJ/cm2 ) 00 On 13.2 溶解性 (分鐘） cn 3 L (S) 6.01 5.78 分子量 Mw 10400 13200 平均單體組成（莫耳％) HAdMA(m-3) (N CN TBMA (m-14) 〇 寸 00 cn α-GBLMA (m-1 ) o o 聚合物 C-B-7 C-B-8 【InfNd 主成分得分 PC3 13.318 9.501 1.579 -8.767 -8.458 -7.173 PC2 -16.785 28.651 -14.793 1.716 1.251 -0.040 PCI -28.621 8.709 47.728 -8.455 -7.852 -11.509 聚合物 C-A-l C-A-2 C-A-3 C-B-l C-B-2 C-B-3 ·Z6I· 201222146 J-a88s 寸 主成分得分 PC3 12.010 8.390 2.380 -8.270 -7.95 -6.560 PC2 16.860 -17.390 -5.300 1.850 1.98 1.980 PC1 -3.740 -12.760 27.110 -3.460 -3.72 -3.810 聚合物 C-A-4 C-A-5 C-A-3 C-B-4 C-B-5 C-B-6 【l&gt;fN&lt;】 主成分得分 PC3 4.656 1.742 1.229 -2.692 -2.358 PC2 0.294 -9.570 10.306 -0.332 -0.253 PCI -12.653 11.700 10.894 -2.840 -3.607 聚合物 C-A-1 C-A-6 C-A-3 C-B-7 C-B-8 201222146 於本實施形態中’根據表22、表23、及表24所示的 結果，可確認與顯影缺陷相關的溶解性、或表示感光度的[inch&lt;N&lt;t_-I sensitivity (mJ/cm2) 00 On 13.2 Solubility (minutes) cn 3 L (S) 6.01 5.78 Molecular weight Mw 10400 13200 Average monomer composition (mol%) HAdMA (m-3 (N CN TBMA (m-14) 〇 inch 00 cn α-GBLMA (m-1 ) oo polymer CB-7 CB-8 [InfNd principal component score PC3 13.318 9.501 1.579 -8.767 -8.458 -7.173 PC2 -16.785 28.651 -14.793 1.716 1.251 -0.040 PCI -28.621 8.709 47.728 -8.455 -7.852 -11.509 Polymer CAI CA-2 CA-3 CBl CB-2 CB-3 ·Z6I· 201222146 J-a88s Inch principal component score PC3 12.010 8.390 2.380 -8.270 -7.95 -6.560 PC2 16.860 -17.390 -5.300 1.850 1.98 1.980 PC1 -3.740 -12.760 27.110 -3.460 -3.72 -3.810 Polymer CA-4 CA-5 CA-3 CB-4 CB-5 CB-6 [l&gt;fN&lt; 】 Principal component score PC3 4.656 1.742 1.229 -2.692 -2.358 PC2 0.294 -9.570 10.306 -0.332 -0.253 PCI -12.653 11.700 10.894 -2.840 -3.607 Polymer CA-1 CA-6 CA-3 CB-7 CB-8 201222146 In the embodiment, according to the results shown in Table 22, Table 23, and Table 24, dissolution associated with development defects can be confirmed. Or represents sensitivity

Eth與評價距離L (S)的值之間存在相關關係，可藉由該 L (S)的值而間接地評價微影製程特性。由此可確認，藉 由本貫施形態的方法，可高精度地進行微影製程特性的間 接的評價。 繼而，當構成共聚合物的單體為n個時，數值轉換部 313 頁示求出貝距離l (s)的式子。於此情況下，因單There is a correlation between Eth and the value of the evaluation distance L (S), and the lithography process characteristics can be indirectly evaluated by the value of L (S). From this, it was confirmed that the indirect evaluation of the lithography process characteristics can be performed with high precision by the method of the present embodiment. Then, when there are n monomers constituting the copolymer, the numerical value conversion unit 313 shows the expression of the Bayer distance l (s). In this case, due to the single

體的種類成為η個，故主成分空間成為晴，於該n維空 間中’僅包含各單體的均聚物的座標點數成為η個，包含 ，部該η個座標點的空間成為W維。因此，評價距離l (S)是求出自評價對象的樣品的座標點至 間為止的評價距離MS)。 ^ 準的二 自該η維空間中的任意的座標點至 離L⑻是將任意的座標點投影於η]維空間止中 求出連結投影於該W維空間巾的表示於η]維 位置的座標點與任意的鍊點的最_測地線的^ 1Since the type of the body is η, the main component space becomes clear, and in the n-dimensional space, the number of coordinates of the homopolymer including only the respective monomers is η, and the space including the η coordinate points becomes W. dimension. Therefore, the evaluation distance l (S) is the evaluation distance MS from the coordinate point of the sample to be evaluated to the interval. ^ The quasi-two from any coordinate point in the n-dimensional space to L(8) is to project an arbitrary coordinate point into the η]-dimensional space to obtain the joint projection in the W-dimensional space towel. The coordinate point and the most _ geodesic of the arbitrary chain point ^ 1

例如，於由第1主成分輪ρ ^ 所形成的η維空間中，长出勺人 η主成分輛pc 如κ 包含各俩聚物的樣品的&amp; 私點（η個主成分得分所示的位置）的W维 Μ 此處，數值轉換部313針對包含單 合物Ο·1至聚合物C-A-n，藉由包含 ^早 絲軸⑽中的座標值（主成分得^各Ί的第U 分她中的座標值(主成分得分)的座標點々 194 201222146For example, in the n-dimensional space formed by the first principal component rotation ρ ^ , the parent η principal component pc such as κ contains the &amp; private point of the sample of each bismer (the η principal component scores are shown) Here, the numerical value conversion unit 313 is for the inclusion of the monom Ο·1 to the polymer CAn, and includes the coordinate value in the early yarn axis (10) (the main component is the U value of each Ί The coordinate point of her coordinate value (principal component score) 々 194 201222146

標點P (A-l)〜座標點P (A-n)。 然後，數值轉換部313藉由以下的式而算出通過座標 點P (A-1)〜座標點P (A-n)的所有點的n-1維空間與 評價對象的共聚合物的座標點P(PC1,PC2, ...，PCn)的評 價距離L (S)。 L (S) —| ajXSPC1 + a2xSPC2 + ... + anxSPCn + an+1 | / ( &amp;i2 + a〗2 + ... + an2) 1/2 於該式中，SPC1為評價對象的共聚合物的第1主成 分軸中的座標值（第1主成分的主成分得分），SPC2為評 價對象的共聚合物的第2主成分軸中的座標值（第2主成 分的主成分得分）、...、SPCn為評價對象的共聚合物的第 η主成分軸中的座標值（第η主成分的主成分得分）。 其中，於算出上述η維的主成分空間中的評價距離L (S )的式中，由 aj XSPC1 -f* &amp;2xSPC2 +... + anxSPCn H- an+1 — 0 的關係所表示的n-1維的比較空間（比主成分空間少 1個維度）通過座標點P (A-1)〜座標點P (A-n)的η 個座標點的所有點。 此處，數值轉換部313是藉由解如下的η元聯立方程 195 201222146 式而算出上述式中的數值（係數）ai至數值an+i，該n元 聯立方程式是將越點Ρ(Α_υ的各座標代人至作為比較 空_ η _ 1 _間的式中而成的η元聯立方程式。 如上所述’於主成分分析部312的處理中，將抗蚀劑 用共聚合物設為S’當該祕劑料聚合物s包含心為 2以上的整數）個構成單元（單體）時，對抗_用共聚 合物S、—及僅包含作料—的構成單元料體的均聚物 C-A-j (卜卜n)的NMR測定中的化學位移與信號強声 枝成分分析，縣出各域分社成分得分pj。因ς 抗姓劑用絲合物s的單體為_，故❹至第ηPunctuation point P (A-l) ~ coordinate point P (A-n). Then, the numerical value conversion unit 313 calculates the n-1 dimensional space passing through all points of the coordinate point P (A-1) to the coordinate point P (An) and the coordinate point P of the copolymer of the evaluation target by the following equation ( The evaluation distance L (S) of PC1, PC2, ..., PCn). L (S) —| ajXSPC1 + a2xSPC2 + ... + anxSPCn + an+1 | / ( &amp;i2 + a〗 2 + ... + an2) 1/2 In this formula, SPC1 is the total of evaluation objects. The coordinate value in the first principal component axis of the polymer (the principal component score of the first principal component), and SPC2 is the coordinate value in the second principal component axis of the copolymer to be evaluated (the principal component score of the second principal component) ), ..., SPCn is a coordinate value (principal component score of the ηth principal component) in the ηth principal component axis of the copolymer to be evaluated. In the equation for calculating the evaluation distance L (S ) in the n-dimensional principal component space, the relationship is represented by the relationship of aj XSPC1 -f* &amp; 2xSPC2 +... + anxSPCn H- an+1 - 0 The n-1 dimensional comparison space (one dimension less than the principal component space) passes through all points of the n coordinate points of the coordinate point P (A-1) to the coordinate point P (An). Here, the numerical value conversion unit 313 calculates the numerical value (coefficient) ai in the above formula to the numerical value an+i by solving the following equation η 201222146, and the n-ary simultaneous equation is to be more η _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ When S' is used as a constituent unit (monomer) in which the polymer s contains a core of 2 or more, the constituents of the anti-composite S, and only the constituent material are contained. The chemical shift in the NMR measurement of the polymer CAj (bab) and the analysis of the strong-sound component of the signal, the scores of the sub-components of the county are pj. Because the monomer for the anti-surname agent filament s is _, so ❹ to the η

Sit上自第1主成分至第11主成分為止)’因此形成η 而且，數值轉換部313將包含η根主成分軸（分 仃的座標軸）Wn維的主成分空間中，均聚物c 成分付分的各個設為各域分轴的座 八 間中的座標點形成。 成刀空 另外，數值轉換部313將包含關於評價對象的彳 物s的主成分得分Pl⑻的點設為座標; ί包έ關於均聚物C-A-j的主成分得分Pi ( A-j)的丄）’ 设為P (A-j)，並算出通過所有座標點p⑷）錢 維空間與座標點P⑻的轉作為評價距離L (S)。11'1)The Sit is formed from the first principal component to the eleventh principal component. Therefore, η is formed. Further, the numerical value conversion unit 313 includes a homopolymer c component in the principal component space including the n-th principal component axis (coordinate axis of the bifurcation) in the Wn dimension. Each of the pay points is formed as a coordinate point in the eight seats of each domain. In addition, the numerical value conversion unit 313 sets a point including the principal component score P1 (8) of the object s of the evaluation target as a coordinate; ί contains a parameter of the principal component score Pi (Aj) of the homopolymer CAj. It is P (Aj), and the rotation of the weight space and the coordinate point P (8) passing through all the coordinate points p (4) is calculated as the evaluation distance L (S). 11'1)

然後，特性評價部314藉由數值轉換部313所 補距離L⑻，而進行評價對象的抗㈣用共聚的 微影製程特性的評價的處理（使用已述的臨限值，。物的 196 201222146Then, the characteristic evaluation unit 314 performs the process of evaluating the lithographic process characteristics for the copolymerization of the evaluation target by the numerical value conversion unit 313 by the distance L (8) (using the threshold value described above, 196 201222146)

配該共聚合物而獲得的抗蝕劑用組成物的微影製程特性的 評價）。 另外，於本實施形態中，以作為包含多種（2種以上） 單體的共聚合物的抗蝕劑用共聚合物的評價為例進行了說 明’但亦可將包括微影製程用共聚合物在内的包含多種單 體的共聚合物作為評價對象，對該些共聚合物的組成中的 單體的排列狀態進行定性評價。Evaluation of the lithographic process characteristics of the composition for a resist obtained by the copolymer. Further, in the present embodiment, the evaluation of a copolymer for a resist which is a copolymer of a plurality of (two or more kinds of monomers) has been described as an example. However, copolymerization including a lithography process may also be included. A copolymer containing a plurality of monomers, including the materials, was used as an evaluation object, and the arrangement state of the monomers in the composition of the copolymers was qualitatively evaluated.

而且’藉由獲取共聚合物的組成中的單體的排列狀態 與包含共聚合物的物性的特性的關聯，即便不實際進行使 用共聚合物的實驗，亦可與抗蝕劑用共聚合物同樣地，根 據評價距離L (S)來推斷共聚合物的特性。 、另外，將用以實現圖2中的波形處理部311、主成分 分析部312、數值轉換部313及特性評價部314的功能的 程式記錄於電腦可讀取的記錄媒體中，使電腦系統讀入、 執行β己錄於5玄5己錄媒體中程式，藉此亦可進行共聚合物的 組成分析的處理。再者，此處所述的「電腦系^」與上述 相同，是指包含OS或周邊機器等硬體者。 —上，參照圖式對本發明的實施形態進行了詳述，但 成並不限定於上述實施形態，亦包㈣脱離該發 明的主旨的範圍的設計等。 【圖式簡單說明】 、圖1是表示利用本發明的一實施形態的共聚合物評價 方法進行絲合物的㈣的絲合物評價0的構成例的 方塊圖。 197 201222146 圖2是表示本發明的一實施形態的共聚合物組成分析 裝置的構成例的方塊圖。 圖3是表示顯示對使3種單體進行聚合而生成的共聚 合物所進行的主成分分析的結果的三維的主成分空間中的 各樣品的座標點的圖。 圖4是表示橫軸為第1主成分軸（PC1)、縱軸為第2 主成分軸（PC2)的包含該第1主成分轴與第2主成分軸 的二維空間的主成分空間的圖。 圖5是表示參考例B-1的結果的圖表。 圖6是表示實例B-1的結果的圖表。 圖7是表示比較例B-1的結果的圖表。 圖8是表示參考例B-2的結果的圖表。 圖9是表示實例B-2的結果的圖表。 圖10是表示參考例B-3的結果的圖表。 圖11是表示實例B-3的結果的圖表。 圖12是表示參考例B-4的結果的圖表。 圖13是表示實例B-4的結果的圖表。 圖14參考例B-5的結果的圖表。 圖15實例B-5的結果的圖表。 圖16是表示參考例B-6的結果的圖表。 圖17是表示實例B-6的結果的圖表。 【主要元件符號說明】 11 :目標變數分析部 12 :波形處理部 198 201222146 nwz-oopif 13 :說明變數分析部 14 :模型生成部 15 :樣品分析部 16 :儲存部 17 :顯示部 18 :控制部 31 :共聚合物組成分析裝置 311 :波形處理部 312 :主成分分析部 313 :數值轉換部 314 :特性評價部 315 : NMR資料儲存部 316 :主成分資料儲存部 350 : NMR測定部 199Further, by obtaining the correlation between the arrangement state of the monomers in the composition of the copolymer and the physical properties of the copolymer, the copolymer for the resist can be used even if the experiment using the copolymer is not actually carried out. Similarly, the characteristics of the copolymer are inferred from the evaluation distance L (S). Further, a program for realizing the functions of the waveform processing unit 311, the principal component analysis unit 312, the numerical value conversion unit 313, and the characteristic evaluation unit 314 in FIG. 2 is recorded on a computer-readable recording medium to read the computer system. The input and execution of β have been recorded in the 5 Xuan 5 recorded media program, whereby the composition analysis of the copolymer can also be performed. In addition, the term "computer system" as used herein refers to a hardware including an OS or a peripheral device. In the above, the embodiment of the present invention has been described in detail with reference to the drawings. However, the present invention is not limited to the above embodiment, and the design (4) of the scope of the gist of the invention is also included. [Brief Description of the Drawings] Fig. 1 is a block diagram showing a configuration example of the evaluation of the linear compound of (4) of the linear compound by the copolymer evaluation method according to the embodiment of the present invention. 197 201222146 Fig. 2 is a block diagram showing a configuration example of a copolymer composition analysis apparatus according to an embodiment of the present invention. Fig. 3 is a view showing coordinate points of respective samples in a three-dimensional principal component space as a result of principal component analysis performed on a copolymer obtained by polymerizing three kinds of monomers. 4 is a principal component space in which a horizontal axis represents a first principal component axis (PC1) and a vertical axis represents a second principal component axis (PC2) in a two-dimensional space including the first principal component axis and the second principal component axis. Figure. Fig. 5 is a graph showing the result of Reference Example B-1. Figure 6 is a graph showing the results of Example B-1. Fig. 7 is a graph showing the results of Comparative Example B-1. Fig. 8 is a graph showing the result of Reference Example B-2. Figure 9 is a graph showing the results of Example B-2. Fig. 10 is a graph showing the results of Reference Example B-3. Figure 11 is a graph showing the results of Example B-3. Fig. 12 is a graph showing the results of Reference Example B-4. Figure 13 is a graph showing the results of Example B-4. Figure 14 is a chart referring to the results of Example B-5. Figure 15 is a graph of the results of Example B-5. Fig. 16 is a graph showing the results of Reference Example B-6. Figure 17 is a graph showing the results of Example B-6. [Description of main component symbols] 11 : Target variable analysis unit 12 : Waveform processing unit 198 201222146 nwz-oopif 13 : Description variable analysis unit 14 : Model generation unit 15 : Sample analysis unit 16 : Storage unit 17 : Display unit 18 : Control unit 31: Copolymer composition analysis device 311: Waveform processing unit 312: Principal component analysis unit 313: Numerical value conversion unit 314: Characteristic evaluation unit 315: NMR data storage unit 316: Principal component data storage unit 350: NMR measurement unit 199

Claims (1)

201222146 七、申請專利範圍： ^ —種微影製程用共聚合物，其是使2種以上的單體 αι〜單體αη (η為2以上的整數）聚合而成、且包含分別 自上述單體αι〜單體αη衍生出的單體單元吣〜單體單元 &lt;的微影製程用共聚合物， 藉由共聚合物的評價方法所算出的單體單元的二 組分率的合計於共聚合物中為2G莫耳％以下，上 物的評價方法是經過下述（1)〜下述（IV)的過程，算^ 表示包ΐ多個上述單體單元的上述共聚合物中的同—種_ _ 的上述單體單元的三單元組於整個組成中所佔的比 述三單元組分率： (I)目標變數分析過程，根據上述單體單元的丘聚人 ,應性比，利用下述計算式（Η)算出作為已知樣：的二 聚合物的組成中的同一種類的上述單體單元的上述三單元 組分率； (Π)說明變數分析過程，根據上述已知樣品的此聚 合物的NMR測定中的化學位移量及信號強度而輸出 變數； 零 、（ΠΟ模型生成過程，藉由部分最小平方回歸而求出 上述目標變數與上述說明變數的回歸模型的回歸式，生成 上述回歸模型的係數；以及 (IV)樣品分析過程’使用上述回歸模型，根據未知 樣品共聚合物的上述NMR測定中的上述化學位移量與上 述信號強度’算出上述未知樣品中的同一種類的上述單體 200 201222146 &quot;TUZ-O opif 單元的上述三單元組分率， [數1] p {J ) j ] (%) = 1 0 0 X [M* j ] x P ( j x P , J · (H) P - [M·/] Γ，~ f[Mh] h:\ rjh ([M’j]是上述共聚合物中的單體單元j的莫耳分率， 於上述單體單元j為上述共聚合物的成長末端的單體單元 時，Pjj是與單體（單元）j進行反應的概率，[Mj]及[Mh] 是反應系統中的各上述單體單元j、h的莫耳分率，rjh是自 上述單體（單元）j至單體（單元）h的共聚合反應性比）。 2. —種微影製程用聚合物的製造方法，其是包括一邊 向反應器内滴加單體及聚合起始劑，一邊於上述反應器内 使2種以上的單體αι〜單體αη (其中，η表示2以上的整 數）進行聚合，而獲得包含單體單元a]〜單體單元α'η (其 中，心〜乂!!表示分別自上述單體α!〜單體αη衍生出的單 體單元）的聚合物（Ρ)的聚合步驟的微影製程用聚合物 的製造方法， 其使用含有上述單體的溶液Sa (a為1〜d，d為1以 上的整數）、溶液Tb (b為1〜e，e為1以上的整數）及溶 液Uc (c為1〜f，f為1以上的整數）， 上述聚合步驟具有分別向上述反應器内供給上述溶液 Sa及上述溶液Tb的主步驟、及於上述主步驟結束後將上 201 201222146 述溶液Uc供給至上述反應器内的後步驟， ❿i述=财，於向上述反應11㈣加上述聚合起始 劑之則、或與開㈣加上述聚合起始_同時 = 應器内開始供給以第丨組成含有 、 述反 述溶液Sa， 成3有上逑早體％〜單體αη的上201222146 VII. Patent application scope: ^—A eutectic process copolymer obtained by polymerizing two or more kinds of monomers α1 to αα (η is an integer of 2 or more) and including the above single The total amount of the two-component ratio of the monomer unit calculated by the evaluation method of the copolymer by the monomer unit 吣~monomer unit derived from the monomer α1 to the monomer αη The copolymer is 2 Gmol% or less, and the evaluation method of the upper material is carried out through the following processes (1) to (IV), and the calculation represents the inclusion of a plurality of the above monomer units in the above-mentioned copolymer. The ratio of the triads of the above-mentioned monomer units of the same type _ _ to the entire composition: (I) target variable analysis process, according to the above-mentioned monomer unit Calculating the above-described three-unit component ratio of the above-mentioned monomer unit of the same kind in the composition of the dipolymer as known by the following calculation formula (Η); (Π) explaining the variable analysis process, according to the above-mentioned The amount of chemical shift in the NMR measurement of this polymer of the sample Signal strength and output variable; zero, (ΠΟ model generation process, the regression equation of the above-mentioned target variable and the above-mentioned explanatory variable is obtained by partial least squares regression to generate the coefficient of the above regression model; and (IV) sample analysis Process 'Using the above regression model to calculate the above-mentioned monomer 200 201222146 &quot;TUZ-O opif unit of the same kind in the above unknown sample based on the above chemical shift amount in the above NMR measurement of the unknown sample copolymer and the above signal intensity ' The above three-unit component ratio, [number 1] p {J ) j ] (%) = 1 0 0 X [M* j ] x P ( jx P , J · (H) P - [M·/] Γ, ~ f[Mh] h:\ rjh ([M'j] is the molar fraction of the monomer unit j in the above copolymer, and the monomer unit j is the monomer unit of the growth end of the above copolymer When Pjj is the probability of reacting with monomer (unit) j, [Mj] and [Mh] are the molar fractions of each of the above monomer units j, h in the reaction system, and rjh is from the above monomer (unit )j to the copolymerization reactivity ratio of the monomer (unit) h) 2. For the lithography process A method for producing a compound comprising adding two or more monomers α1 to αα in the reactor while dropping a monomer and a polymerization initiator into the reactor (where η represents 2 or more) The polymerization is carried out to obtain a polymer comprising the monomer unit a] to the monomer unit α'η (wherein, the core ~乂!! represents the monomer unit derived from the above monomer α!~ monomer αη) (Ρ) a method for producing a lithographic process polymer, which uses a solution Sa containing the above monomer (a is 1 to d, d is an integer of 1 or more), and a solution Tb (b is 1 to e, e is an integer of 1 or more) and a solution Uc (c is 1 to f, and f is an integer of 1 or more), and the polymerization step has a main step of supplying the solution Sa and the solution Tb to the reactor, respectively After the main step is completed, the step 201 201222146 is supplied to the reactor in the subsequent step, wherein the polymerization initiator is added to the reaction 11 (four), or the polymerization start is added to the reaction (4). At the same time, the supply is started in the device, and the composition is contained in the third Solution Sa, there are 3 to the body early K.% on the monomers αη ^上述反應器_始供給上述溶液&amp;之後 始述溶液Sa的同時，向上述反應器内開始滴加^ ，且成3有上述單體αι〜單體αη的上述溶液Tb，且 液Sa的供給於上述溶液Tb的滴加結束之前姓束，冷 ~ 聚合物（p)t社料體單元心 早體早的含有比率的目標組成（單位：莫耳 αι · α2 . ..· : a，na寺， 作為上述溶液T1〜溶液Te各自的上述賴的組 第2組成與上述目標組成相同， 、 曰容液S1〜騎Sd各自的上述單體的組成與上述 目 不同，作為上述溶液S1〜溶液％的合計^The above reactor_ is supplied to the above solution &amp; and then the solution Sa is started, and the above solution Tb is started to be added to the above reactor, and the above solution Tb of the above monomer α1 to monomer αη is formed, and the liquid Sa is The target composition before the end of the dropwise addition of the above solution Tb, the target composition of the cold-polymer (p)t community unit early phase of the body (unit: moel αι · α2 . . . . : a, In the na temple, the second composition of the above-mentioned group of the solution T1 to the solution Te is the same as the above-described target composition, and the composition of the monomer of each of the buffer liquids S1 to Sd is different from the above, and the solution S1 is Total of solution % =體的組成的第〗組成是上述單體α]〜單體％之中，丘聚 :反應速度最慢的上述單體的比例多於上述目標組成的组 成， ， j後步财’上述溶液m〜溶液Uf各自的上述單 τ ^ίΐ與上述目標組成不同，作為上述溶液U1〜溶液 、口计的上述單體的組成的第3組成是上述單體％〜單 η之中共聚合反應速度最慢的上述單體的比例少於上 述目標組成的组成。 ' 202 201222146 -rw^ooyif 3.如申請專利範圍第 製造方法，射當表示欲與1之微影製程用聚合物的 述單體單元（〜單體單元Ύ、述聚合物（P)尹的上 C單位：莫耳％)為乂 ·αα·η、έ有比率的上述目#租成 作為上述絲I麵 含 的含有比各上述單體單元 計量 、（υ首先，以固定的滴加速度，二 :目^二:α’2:...: α，η相同:單體3混合物 上述溶加溶液滴加至僅加入* 為“、t2、t3...時，求出分別;起的經過時間 =〜單體.的組成(單位:莫耳二應:内的上:單 及自^至匕為止的期間、自 2.….Mn， 生成的聚合物中的上述單體單元二單體^間、内分別 (單位：莫耳％) Pl : p2: · : p ; 早疋αη的比率 ^： Tt 7Pn a α，1 ^ 上的整數）」； m tm+1為止的期間（m為1以 ρ2: (3)Λ1 上1「自tm〜為止的期間」内的〜 …n0H__tm_Ml、：.··：_ 203 201222146 值，藉由下述式而求出因數 = P2/M2、...Fn==Pn/Mn;以及 2、··. n’F产Pl/Ml、F2 (4)若以 αιι: . 莫耳％)、以Fl、F、 主·」αΐη表示s’a的組成（單位： 則= 0^ τ上述（3)中所求出的因數， 1 ai2-a2/F2、..·αΐη==α，/；ρ。 4.如申請專利範圍第2 η η、The composition of the body composition is the above-mentioned monomer α]~ monomer%, the polycondensation: the reaction rate of the slowest of the above monomers is more than the composition of the above target composition, j after the step of 'the above solution The above-mentioned single τ ΐ 各自 of each of the m~ solution Uf is different from the above-mentioned target composition, and the third composition of the composition of the above-mentioned monomer as the solution U1 to the solution and the mouth is the copolymerization reaction rate among the above monomers % to η. The proportion of the above monomers which are slow is less than the composition of the above target composition. ' 202 201222146 -rw^ooyif 3. As described in the patent application scope, the monomer unit (the monomer unit Ύ, the polymer (P) Yin which is intended to be used with the lithography process of 1 The upper C unit: the molar %) is the above-mentioned mesh of the ratio of 乂·αα·η, έ, and the content of the above-mentioned silk I surface is measured as compared with each of the above-mentioned monomer units, (first, at a fixed drip rate, Two: Objective ^2: α'2:...: α, η are the same: monomer 3 mixture The above solution is added dropwise to add only * for ", t2, t3..., find the difference; After the time = ~ monomer. The composition (unit: Mo Er Er: inside the upper: single and from ^ to 匕 period, from 2... Mn, the above monomer unit in the resulting polymer Between the body and the inside (unit: mole %) Pl : p2: · : p ; ratio of early 疋αη^: Tt 7Pn a α, integer on 1 ^)"; period until m tm+1 (m For the value of 1 ... n0H__tm_Ml, :.·:: 203 201222146 in 1 "period from tm~" on ρ2: (3) Λ1, the factor = P2/M2 is obtained by the following equation. ..Fn==Pn/Mn ; and 2,···. n'F produces Pl/Ml, F2 (4) if αιι: . Mole%), Fl, F, main ·"αΐη represents the composition of s'a (unit: then = 0 ^ τ The factor obtained in (3) above, 1 ai2-a2/F2, ..·αΐη==α, /; ρ. 4. As in the patent application range 2 η η, 聚合物的製造方法，Μ ^ 3賴狀微影製程用 中的上述單體單元.H示欲述聚合物⑺ 標組成（單位：莫耳…爲體早％ a』含有比率的上述目 你盔 。馮α 1 . a、：…：α'η時， 的第3組成=單：元 上述單體的組成 方法+、早體早兀的含有比率分別為藉由下述 的含有比車⑴所求出的Ue中的各上述單體單元 的4比率的值的〇.8倍〜12倍的範圍内： 組成a，5 .以固定的滴加速度’將含有單體組成與上述目標 述聚人=1· ···:(相同的單體混合物刚質量份、上 劑的Iΐ，溶劑的滴加溶液滴加至僅加人有上述溶 t Ί w器内，當自滴加開始算起的經過時間為tl、 丄單=.0、’求出分別殘存於上述反應器内的上述單體山 =〜的組成（單位：莫耳％)地：以2:...:1^，及 成的平上f止的期間、自t2至t3為止的期間、...内分別生 位.、直i +的上述單體單元°1，1〜單體單元a’n的比率（單 位.莫耳％) P】· P2: : Pn ; ⑷找出上述？1:1&gt;2: ... :Pn最接近上述目標組成心： 2 ··· an的時段「自‘至“為止的期間為1以 204 201222146 ^fUZ-OOpif 上的整數）J; (7 )根據上述「自tm至tm+ i為止的期間」内的: P2 : : Pn的值、及經過時間tm内的Ml : M2 :…：Mn的 值，藉由下述式而求出因數Fi、？2、...Fn，、F2 = P2/M2、...Fn^Pn/Mn ;以及The method for producing a polymer, the above monomer unit in the process of 微 3 微 微 . . . 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 盔 盔 盔 盔 盔Von α 1 . a, :...: α'η, the third composition = single: the composition method of the above monomer +, the content ratio of the early body early 兀 is respectively by the following content ratio vehicle (1) The value of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the above-mentioned monomer to the above-mentioned target =1····: (The same monomer mixture is just the mass part, the I 上 of the upper agent, and the solvent addition solution is added dropwise to the person who has only the above-mentioned dissolved Ί , w, starting from the start of the dropwise addition The elapsed time is tl, 丄 = = .0, 'determine the composition (unit: mol%) of the above-mentioned monomer mountain = ~ remaining in the above reactor: 2:...:1^, and The ratio of the above-mentioned monomer unit °1,1 to the monomer unit a'n in the period from the time t2 to t3, the period from t2 to t3, and the ratio of the monomer unit to the monomer unit a'n. Mo Ear %) P]· P2: : Pn ; (4) Find the above? 1:1&gt;2: ... :Pn is closest to the above target composition: 2 ··· an period from "from" to " 1 to 204 201222146 ^fUZ-OOpif integer) J; (7) According to the above "period from tm to tm + i": P2: : Pn value, and M1 in the elapsed time tm : M2 :... : Mn value, the factors Fi, ?2, ... Fn, F2 = P2 / M2, ... Fn ^ Pn / Mn are obtained by the following formula; (8)砮以α31 : α32 :…：α3η表示u'c的組成（單位： 莫耳％)、以Fi、F2、…Fn (其中’將中的最小者替 換為0)表示上述（7)中所求出的因數，則a31 = a，lXFl/ (a’ixFi + a'2xF2 + ... + a'nxFn )、a32 = a’2xF2/ ( a'xF! + a，2xF2 + . _ · + a’nxFn )、…a3n = a'nxFn/ ( a、％ + a'2xF2 + ·.. + a’nxFn)。 5. —種微影製程用聚合物’其藉由如申請專利範圍第 2項所述之微影製程用聚合物的製造方法而獲得。 6. —種抗蝕劑組成物，其含有如申請專利範圍第j項 或第5項所述之微影製程用聚合物、及藉由光化射線或放 射線的照射而產生酸的化合物。 一種形成有圖案的基板的製造方法，其包括 將如申請專利範圍第6項所述之抗蝕劑組成物塗佈於 基板的被加工面上而形成抗蝕膜的步驟； 對上述抗蝕膜進行曝光的步驟；以及 =顯影液對經曝光的上述抗_進行顯影的步驟。 以上的聚合物的評價方法，其是算出表示包含2種 體單元的：的共聚合物的組成巾的同—種類的上述單 早的二平歧於整個組成中所佔的比例的三單元組分 205 201222146 率的共聚合物的評價方法，其包括： 目標變數分析過程，目標變數分析部 元的共聚合反應性比，_下述計算式（H) 4 =早 知樣品的共聚合物的組成中的同—種類 I :已 上述三單元組分率； 』上述早體早兀的 說明變數分析過程，說明變數分析部根 品的共聚合物的職測定中的化 二= 輸出說明變數； 錢域強度而 、模型生成過程，模型生成部藉由部分最小平方 求出上述目標變數與上述說明變數的回歸模型的 生成上述回歸模型的係數；以及 工 」品分析過程，樣品分析部使用上述回歸模型，根據 未知樣品共聚合述NMR狀巾的上述化學位 ，上述信賴度’算出未知樣品__—_的上 早元的上述三單元組分率； [數2] P(j p j ) (%) =ί 1 Ο 〇 X [Μ· ^βι Ρ Ρ (Η) ([Mj]Tc上述共聚合物中的單體單元』的莫耳分率， ;上述單體單元j為上述共聚合物的成長末端的單體單元 夺疋與單體（單元）j進行反應的概率，[%]及[Mh] 206 201222146 nuz.oopif 是反，系統中的各上述單體單〜、h的莫耳分率，r 上述單體（單元）j至單髀〔罝-、 此疋自 〇二j早體（早凡）h的共聚合反應性比）。 .-種，、聚合物組成分㈣法，其是共聚合物 體皁元的排舰態的絲合物組成分析方法，其包括：早 測定資料提取過程，測定資料提取部自上 的NMR光譜’將包含構成上述共聚合物的上述單(8) α is α31 : α32 :...: α3η represents the composition of u'c (unit: mole %), and Fi, F2, ... Fn (where 'the smallest of 'will be replaced by 0) means the above (7) The factor found in a31 = a, lXFl / (a'ixFi + a'2xF2 + ... + a'nxFn ), a32 = a'2xF2/ ( a'xF! + a, 2xF2 + . _ · + a'nxFn ),...a3n = a'nxFn/ ( a, % + a'2xF2 + ·.. + a'nxFn). 5. A lithographic process polymer, which is obtained by the method for producing a lithographic process polymer according to claim 2 of the patent application. A resist composition comprising the lithographic process polymer according to item j or item 5 of the patent application, and a compound which generates an acid by irradiation with actinic rays or radiation. A method for producing a patterned substrate, comprising the steps of: applying a resist composition according to claim 6 of the invention to a processed surface of a substrate to form a resist film; a step of performing exposure; and = a step of developing the exposed anti-reflection solution by the developer. The above-mentioned method for evaluating a polymer is a three-unit group in which the ratio of the above-mentioned single early two-division in the entire composition of the same type of the composition of the copolymer containing the two kinds of the unit cells is calculated. A method for evaluating a copolymer of 205 201222146, which comprises: a target variable analysis process, a copolymerization reactivity ratio of a target variable analysis unit, _ the following calculation formula (H) 4 = a copolymer of a prior-known sample The same type I in the composition: the above-mentioned three-unit component ratio; 』 The above-mentioned early body early description of the variable analysis process, indicating the variation of the co-polymer of the root of the variable analysis section = the output explanatory variable; In the money domain intensity and the model generation process, the model generation unit obtains the coefficient of the regression model by using the partial least squares to obtain the regression coefficient of the target variable and the explanatory variable described above; and the sample analysis process, and the sample analysis unit uses the above regression a model in which the above-mentioned chemical position of the NMR-like towel is copolymerized according to an unknown sample, and the above-mentioned reliability 'calculates the above-mentioned three of the early samples of the unknown sample ____ Unit component ratio; [Number 2] P(jpj ) (%) = ί 1 Ο 〇X [Μ· ^βι Ρ Ρ (Η) ([Mj]Tc monomer unit in the above copolymer] Fraction, the above monomer unit j is the probability that the monomer unit of the growth end of the above-mentioned copolymer polymer reacts with the monomer (unit) j, [%] and [Mh] 206 201222146 nuz.oopif is reversed, The molar fraction of each of the above monomers in the system, h, r the copolymerization reactivity of the above monomer (unit) j to monoterpene [罝-, 疋 疋 j j 早 早 早 早 早 早ratio). .-, polymer composition (four) method, which is a method for analyzing the composition of the silk-like structure of the copolymerized soap element, which comprises: early determination of the data extraction process, and determination of the NMR spectrum from the upper part of the data extraction section' Will contain the above-mentioned single sheet constituting the above-mentioned copolymer ^波長的範_上述NMR綠作為共聚合物測定資料而 ^取， 主成分分_程’域分分析料行對於上述共聚合 物測疋資料、及上述單體各自的上述NMR光譜的單體 疋身，的化學位移及光譜強度的主成分分析，直至對應於 i述單^，量Π(η為2以上的整數）的第n主成分^止; 距離算出過程，數值轉換部求出上述第1主成分至上 述第η主成分的主成分軸所構成的n維的主成分空間中， 自包含所有上社成錄巾的上料體的域分得分所表 示的座=闕n_l _錄空間，至上述共聚合物的上述 主成分得分所表示的對象座標點為止的評價距離；以及 特性評價過程，特性評價部藉由上述評價距離而評價 上述共聚合物的特性。 10. —種共聚合物的製造方法，其包括： 使2種以上的單體進行聚合而獲得共聚合物的步驟； 以及 藉由如申睛專利範圍第8項所述之共聚合物的評價方 法，對所獲得的上述共聚合物進行評價的步驟。 207 201222146 11. 一種共聚合物的製造方法，其包括： 使2種以上的單體進行聚合而獲得共聚合物的步驟； 以及 藉由如申請專利範圍第9項所述之共聚合物組成分析 方法，對所獲得的上述共聚合物進行分析的步驟。^The range of the wavelength_the above NMR green is taken as the copolymer measurement data, and the main component is divided into the domain analysis data for the above-mentioned copolymer measurement data, and the monomer of the above NMR spectrum of the above monomers. Principal component analysis of the chemical shift and the spectral intensity of the body, until the nth principal component corresponding to the 述 ,, Π (η is an integer of 2 or more); the distance calculation process, the numerical conversion unit obtains the above In the n-dimensional principal component space composed of the main component axis of the first principal component to the nt principal component, the block indicated by the domain score of the upper body including all the Shangshecheng towels is recorded as 座n_l_record The space is an evaluation distance from the target coordinate point indicated by the principal component score of the above-mentioned copolymer; and the characteristic evaluation process, the characteristic evaluation unit evaluates the characteristics of the copolymer by the evaluation distance. 10. A method for producing a copolymer comprising: a step of polymerizing two or more kinds of monomers to obtain a copolymer; and an evaluation of a copolymer as described in claim 8 A method of evaluating the obtained copolymer described above. 207 201222146 11. A method for producing a copolymer comprising: a step of polymerizing two or more kinds of monomers to obtain a copolymer; and an analysis of a copolymer composition as described in claim 9 Method, the step of analyzing the obtained copolymer described above. 208208
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